Ethylene-based polymer compositions for use as a blend component in shrinkage film applications

ABSTRACT

An ethylene-based polymer composition has been discovered and is characterized by a Comonomer Distribution Constant greater than about 45. The new ethylene-based polymer compositions are useful for making many articles, especially including films. Formulations made into films comprising the new polymers are also disclosed, especially blends with synthetic polymer like LDPE where the % LDPE is less than 50% in which the MD shrink tension is greater than 15 cN, puncture is greater than 75 ft-lb/in 3 , and haze is less than 20%. The polymers are made using a metal complex of a polyvalent aryloxyether.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. provisional patent application Ser. No. 61/222,371, filed Jul. 1, 2009, the disclosure of which is incorporated herein by reference for purposes of U.S. practice.

BACKGROUND OF THE INVENTION

There have been many varieties of polyethylene polymers polymerized over the years, including those made using high pressure free radical chemistry (LDPE), more traditional linear low density polyethylene (LLDPE) typically made using Ziegler-Natta catalysis or metallocene or constrained geometry catalyzed polyethylene. Some linear polyethylenes, but also some substantially linear polyethylenes, contain a slight amount of long chain branching. While these polymers have varying positives and negatives—depending on application or end-use—more control over the polymer structure is still desired.

We have now found that post-metallocene catalysts can efficiently polymerize ethylene into polymers and polymer compositions having controlled comonomer distribution profiles, while also controlling unsaturation levels in the polymer.

SUMMARY OF THE INVENTION

In one embodiment, the invention is an ethylene-based polymer composition characterized by a Comonomer Distribution Constant greater than about 45 and as high as 400, wherein the composition has less than 120 total unsaturation unit/1,000,000 C, wherein the composition is further characterized as comprising a MW Ratio at each temperature is less than or equal to 1.00 for each fraction comprising more than 1.0 wt % which represents the area of the fraction divided by the total area of all fractions, preferably where the MW Ratio increases with the temperature of each fraction and also preferably wherein the MW Ratio is less than 0.10 for each temperature that is equal to or lower than 50° C. Preferably, the composition further comprises a melt index of less than or equal to 0.90 g/10 min and/or a density of less than 0.945 g/cc and greater than 0.92 g/cc, preferably greater than 0.92 g/cc and less than 0.94 g/cc.

The cumulative weight fraction can be less than 0.10 for the fractions with a temperature up to 50° C. and preferably the cumulative weight fraction is not less than 0.03 for the fractions with a temperature up to 85° C.

The compositions can be further characterized as comprising:

-   -   (a) one Component A being 20-65 wt % of the composition with a         MI less than 0.3 and has a higher density than Component B with         a density difference between Component B and A of greater than         0.005 g/cc     -   (b) Component B having a MI greater than that of Component A     -   (c) With the overall polymer having a MI of less than or equal         to 0.9 and a density of less than 0.945 g/cc and greater than         0.92 g/cc.         The compositions can comprise up to about 3 long chain         branches/1000 carbons and can have a ZSVR of at least 2.5,         preferably at least 4. The compositions can be further         characterized by comprising less than 20 vinylidene unsaturation         unit/1,000,000 C and/or by comprising less than 20         trisubstituted unsaturation unit/1,000,000 C. The compositions         can also have a bimodal molecular weight distribution and/or         comprise a single DSC melting peak.

Fabricated articles comprising the compositions are also contemplated, especially at least one film layer, as are thermoplastic formulations comprising the compositions and at least one natural or synthetic polymer, especially wherein the synthetic polymer is LDPE and the % LDPE is greater than 30% in which in which a blown film comprising the formulation has a MD shrink tension is greater than 15 cN, puncture is greater than 60 ft-lb/in³, and haze is less than 20%. The compositions can be at least partially cross-linked (at least 5 wt % gel). The compositions can have a comonomer distribution profile comprising a mono or bimodal distribution from 35° C. to 120° C., excluding the purge and can also have a Mw from about 80,000 to about 200,000 g/mol.

The polymer compositions can be characterized as having a ratio of viscosity at 190° C. at 0.1 rad/s to a viscosity at 190° C. at 100 rad/s of greater than 8.5 as determined by dynamic mechanical spectroscopy and/or characterized as having a phase angle of less than 65 degrees and greater than 0 degrees at a complex modulus of 10,000 Pa as determined by dynamic mechanical spectroscopy at 190° C. The polymer compositions can also be characterized as having a M_(w)/M_(n) less than 10 and preferably less than 4, but greater than 2.

In another embodiment, the invention is a process comprising:

(A) polymerizing ethylene in the presence of a first catalyst to form a semi-crystalline ethylene-based polymer in a first reactor or a first part of a multi-part reactor; and

(B) reacting the semi-crystalline ethylene-based polymer with additional ethylene in the presence of a second catalyst to form an ethylenic polymer in at least one other reactor or a later part of a multi-part reactor, wherein the catalyst of (A) and (B) can be the same or different and each is a metal complex of a polyvalent aryloxyether corresponding to the formula:

where M³ is Ti, Hf or Zr, preferably Zr;

Ar⁴ independently each occurrence is a substituted C₉₋₂₀ aryl group, wherein the substituents, independently each occurrence, are selected from the group consisting of alkyl; cycloalkyl; and aryl groups; and halo-, trihydrocarbylsilyl- and halohydrocarbyl-substituted derivatives thereof, with the proviso that at least one substituent lacks co-planarity with the aryl group to which it is attached;

T⁴ independently each occurrence is a C₂₋₂₀ alkylene, cycloalkylene or cycloalkenylene group, or an inertly substituted derivative thereof;

R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or di(hydrocarbyl)amino group of up to 50 atoms not counting hydrogen;

R³ independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen, or two R³ groups on the same arylene ring together or an R³ and an R²¹ group on the same or different arylene ring together form a divalent ligand group attached to the arylene group in two positions or join two different arylene rings together; and

R^(D), independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R^(D) groups together are a hydrocarbylene, hydrocarbadiyl, diene, or poly(hydrocarbyl)silylene group, especially where the reaction of step (B) occurs by graft polymerization.

BRIEF DESCRIPTION OF THE DRAWINGS

For the purpose of illustrating the invention, there is shown in the drawings a form that is exemplary; it being understood, however, that this invention is not limited to the precise arrangements and instrumentalities shown.

FIG. 1 is comonomer distribution profile for Example 1;

FIG. 2 is ¹H NMR integral regions for unsaturation;

FIG. 3 is dynamical mechanical spectroscopy complex viscosity data versus frequency for Examples and Comparative Examples;

FIG. 4 is dynamical mechanical spectroscopy tan delta data versus frequency for Examples and Comparative Examples;

FIG. 5 is dynamical mechanical spectroscopy data plot of phase angle vs. complex modulus (Van-Gurp Palmen plot) for Examples and Comparative Examples;

FIG. 6 is melt strength data at 190° C. of 0.5 MI type samples: Examples 1, 2, 3, and 7 and Comparative Example 2;

FIG. 7 is melt strength data at 190° C. of 0.85 MI type samples: Examples 4, 5, 6, and 8 and Comparative Example 1;

FIG. 8 is conventional GPC plot for Examples 1-5;

FIG. 9 is conventional GPC plot for Examples 6-8 and Comparative Examples 1-2;

FIG. 10 is CEF plot for Examples 1-4 and Comparative Example 1;

FIG. 11 is CEF plot for Examples 5-8 and Comparative Example 2;

FIG. 12 is MW Ratio plot for Examples 1-4 and Comparative Examples 1-2; and

FIG. 13 is MW Ratio plot for Examples 5-8 and Comparative Examples 1-2.

DETAILED DESCRIPTION OF THE INVENTION

In some processes, processing aids, such as plasticizers, can also be included in the ethylenic polymer product. These aids include, but are not limited to, the phthalates, such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin, and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins from rosin or petroleum feedstocks. Exemplary classes of oils useful as processing aids include white mineral oil such as KAYDOL oil (Chemtura Corp.; Middlebury, Conn.) and SHELLFLEX 371 naphthenic oil (Shell Lubricants; Houston, Tex.). Another suitable oil is TUFFLO oil (Lyondell Lubricants; Houston, Tex.).

In some processes, ethylenic polymers are treated with one or more stabilizers, for example, antioxidants, such as IRGANOX 1010 and IRGAFOS 168 (Ciba Specialty Chemicals; Glattbrugg, Switzerland). In general, polymers are treated with one or more stabilizers before an extrusion or other melt processes. In other embodiment processes, other polymeric additives include, but are not limited to, ultraviolet light absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, fire retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents and anti-blocking agents. The ethylenic polymer composition may, for example, comprise less than 10 percent by the combined weight of one or more additives, based on the weight of the embodiment ethylenic polymer. A particular benefit of the claimed polymers is the absence of catalyst kill agents, other than water, thus eliminating the need for calcium stearate.

The ethylenic polymer produced may further be compounded. In some ethylenic polymer compositions, one or more antioxidants may further be compounded into the polymer and the compounded polymer pelletized. The compounded ethylenic polymer may contain any amount of one or more antioxidants. For example, the compounded ethylenic polymer may comprise from about 200 to about 600 parts of one or more phenolic antioxidants per one million parts of the polymer. In addition, the compounded ethylenic polymer may comprise from about 800 to about 1200 parts of a phosphite-based antioxidant per one million parts of polymer. The compounded disclosed ethylenic polymer may further comprise from about 300 to about 1250 parts of calcium stearate per one million parts of polymer.

Uses

The ethylenic polymer may be employed in a variety of conventional thermoplastic fabrication processes to produce useful articles, including objects comprising at least one film layer, such as a monolayer film, or at least one layer in a multilayer film prepared by cast, blown, calendered, or extrusion coating processes; molded articles, such as blow molded, injection molded, or rotomolded articles; extrusions; fibers; and woven or non-woven fabrics. Thermoplastic compositions comprising the ethylenic polymer include blends with other natural or synthetic materials, polymers, additives, reinforcing agents, ignition resistant additives, antioxidants, stabilizers, colorants, extenders, crosslinkers, blowing agents, and plasticizers.

The ethylenic polymer may be used in producing fibers for other applications. Fibers that may be prepared from the ethylenic polymer or blends thereof include staple fibers, tow, multicomponent, sheath/core, twisted, and monofilament. Suitable fiber forming processes include spunbonded and melt blown techniques, as disclosed in U.S. Pat. No. 4,340,563 (Appel, et al.), U.S. Pat. No. 4,663,220 (Wisneski, et al.), U.S. Pat. No. 4,668,566 (Nohr, et al.), and U.S. Pat. No. 4,322,027 (Reba), gel spun fibers as disclosed in U.S. Pat. No. 4,413,110 (Kavesh, et al.), woven and nonwoven fabrics, as disclosed in U.S. Pat. No. 3,485,706 (May), or structures made from such fibers, including blends with other fibers, such as polyester, nylon or cotton, thermoformed articles, extruded shapes, including profile extrusions and co-extrusions, calendared articles, and drawn, twisted, or crimped yarns or fibers.

Additives and adjuvants may be added to the ethylenic polymer post-formation. Suitable additives include fillers, such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, including carbon fibers, silicon nitride fibers, steel wire or mesh, and nylon or polyester cording, nano-sized particles, clays, and so forth; tackifiers, oil extenders, including paraffinic or napthelenic oils; and other natural and synthetic polymers, including other polymers that are or can be made according to the embodiment methods.

Blends and mixtures of the ethylenic polymer with other polyolefins may be performed. Suitable polymers for blending with the embodiment ethylenic polymer include thermoplastic and non-thermoplastic polymers including natural and synthetic polymers. Exemplary polymers for blending include polypropylene, (both impact modifying polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene/propylene copolymers), various types of polyethylene, including high pressure, free-radical low density polyethylene (LDPE), Ziegler-Natta linear low density polyethylene (LLDPE), metallocene PE, including multiple reactor PE (“in reactor” blends of Ziegler-Natta PE and metallocene PE, such as products disclosed in U.S. Pat. No. 6,545,088 (Kolthammer, et al.); U.S. Pat. No. 6,538,070 (Cardwell, et al.); U.S. Pat. No. 6,566,446 (Parikh, et al.); U.S. Pat. No. 5,844,045 (Kolthammer, et al.); U.S. Pat. No. 5,869,575 (Kolthammer, et al.); and U.S. Pat. No. 6,448,341 (Kolthammer, et al.)), ethylene-vinyl acetate (EVA), ethylene/vinyl alcohol copolymers, polystyrene, impact modified polystyrene, Acrylonitrile-Butadiene-Styrene (ABS), styrene/butadiene block copolymers and hydrogenated derivatives thereof (Styrene-Butadiene-Styrene (SBS) and Styrene-Ethylene-Butadiene-Styrene (SEBS), and thermoplastic polyurethanes. Homogeneous polymers such as olefin plastomers and elastomers, ethylene and propylene-based copolymers (for example, polymers available under the trade designation VERSIFY™ Plastomers & Elastomers (The Dow Chemical Company), SURPASS™ (Nova Chemicals), and VISTAMAXX™ (ExxonMobil Chemical Co.)) can also be useful as components in blends comprising the ethylenic polymer.

The ethylenic polymer maybe employed as sealant resins. Surprisingly, certain short chain branching distribution (SCBD), as shown by Comonomer Distribution Constant (CDC), in combination with certain molecular weight distribution (MWD), and a certain level of long chain branching (LCB) has shown to improve hot tack and heat seal performance, including increased hot-tack & heat-seal strength, lower heat seal and hot tack initiation temperatures, and a broadening of the hot tack window. The ethylenic polymer may be employed as a pipe and tubing resin through an optimization of the SCBD and MWD, with low unsaturation levels for improved ESCR (environmental stress crack resistance) and higher PENT (Pennsylvania Edge-Notch Tensile Test). The ethylenic polymer may be employed in applications where ultraviolet (UV) stability, and weatherability are desired through an optimization of the SCBD and MWD, in combination with low unsaturation levels, and low levels of low molecular weight, high comonomer incorporated oligomers. The ethylenic polymer may be employed in applications where low levels of plate-out, blooming, die build-up, smoke formation, extractables, taste, and odor are desired through an optimization of the SCBD and MWD with low levels of low molecular weight, high comonomer incorporated oligomers. The ethylenic polymer may be employed in stretch film applications. Surprisingly, certain SCBD, in combination with certain MWD, and a certain level of long chain branching (LCB) shows improved stretchability and dynamic puncture resistance.

DEFINITIONS

The term “composition,” as used, includes a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

The terms “blend” or “polymer blend,” as used, mean an intimate physical mixture (that is, without reaction) of two or more polymers. A blend may or may not be miscible (not phase separated at molecular level). A blend may or may not be phase separated. A blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art. The blend may be affected by physically mixing the two or more polymers on the macro level (for example, melt blending resins or compounding) or the micro level (for example, simultaneous forming within the same reactor).

The term “linear” refers to polymers where the polymer backbone of the polymer lacks measurable or demonstrable long chain branches, for example, the polymer can be substituted with an average of less than 0.01 long branch per 1000 carbons.

The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer, and the term “interpolymer” as defined. The terms “ethylene/α-olefin polymer” is indicative of interpolymers as described.

The term “interpolymer” refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different types of monomers.

The term “ethylene-based polymer” refers to a polymer that contains more than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and, optionally, may contain at least one comonomer.

The term “ethylene/α-olefin interpolymer” refers to an interpolymer that contains more than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and at least one α-olefin.

The term “ethylenic polymer” refers to a polymer resulting from the intermolecular bonding of a crystalline ethylene-based polymer and at least one highly long chain branched ethylene-based polymer.

Test Methods Density

Samples that are measured for density are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792, Method B.

Melt Index

Melt index, MI or I₂, is measured in accordance with ASTM D 1238, Condition 190° C./2.16 kg, and is reported in grams eluted per 10 minutes. I₁₀ is measured in accordance with ASTM D 1238, Condition 190° C./10 kg, and is reported in grams eluted per 10 minutes.

DSC Crystallinity

Differential Scanning Calorimetry (DSC) can be used to measure the melting and crystallization behavior of a polymer over a wide range of temperature. For example, the TA Instruments Q1000 DSC, equipped with an RCS (refrigerated cooling system) and an autosampler is used to perform this analysis. During testing, a nitrogen purge gas flow of 50 L/min is used. Each sample is melt pressed into a thin film at about 175° C.; the melted sample is then air-cooled to room temperature (˜25° C.). A 3-10 mg, 6 mm diameter specimen is extracted from the cooled polymer, weighed, placed in a light aluminum pan (ca 50 mg), and crimped shut. Analysis is then performed to determine its thermal properties.

The thermal behavior of the sample is determined by ramping the sample temperature up and down to create a heat flow versus temperature profile. First, the sample is rapidly heated to 180° C. and held isothermal for 3 minutes in order to remove its thermal history. Next, the sample is cooled to −40° C. at a 10° C./minute cooling rate and held isothermal at −40° C. for 3 minutes. The sample is then heated to 150° C. (this is the “second heat” ramp) at a 10° C./minute heating rate. The cooling and second heating curves are recorded. The cool curve is analyzed by setting baseline endpoints from the beginning of crystallization to −20° C. The heat curve is analyzed by setting baseline endpoints from −20° C. to the end of melt. The values determined are peak melting temperature (T_(m)), peak crystallization temperature (T_(a)), heat of fusion (H_(f)) (in Joules per gram), and the calculated % Crystallinity for polyethylene samples using Equation (1):

% Crystallinity=((H _(f))/(292 J/g))×100  (Eq. 1)

The heat of fusion (H_(f)) and the peak melting temperature are reported from the second heat curve. Peak crystallization temperature is determined from the cooling curve.

Dynamic Mechanical Spectroscopy (DMS) Frequency Sweep

Resins were compression-molded into 3 mm thick×1 inch circular plaques at 350° F. for 5 minutes under 1500 psi pressure in air. The sample is then taken out of the press and placed on the counter to cool.

A constant temperature frequency sweep is performed using a TA Instruments “Advanced Rheometric Expansion System (ARES),” equipped with 25 mm parallel plates, under a nitrogen purge. The sample is placed on the plate and allowed to melt for five minutes at 190° C. The plates are then closed to 2 mm, the sample trimmed, and then the test is started. The method has an additional five minute delay built in, to allow for temperature equilibrium. The experiments are performed at 190° C. over a frequency range of 0.1 to 100 rad/s. The strain amplitude is constant at 10%. The stress response is analyzed in terms of amplitude and phase, from which the storage modulus (G′), loss modulus (G″), complex modulus (G*), dynamic viscosity η*, and tan (δ) or tan delta are calculated.

CEF Method

Comonomer distribution analysis is performed by Crystallization Elution Fractionation (CEF) (PolymerChar in Spain) (B. Monrabal et al, Macromol. Symp. 257, 71-79 (2007)). Ortho-dichlorobenzene (ODCB) with 600 ppm antioxidant butylated hydroxytoluene (BHT) is used as the solvent. Sample preparation is done with an autosampler at 160° C. for 2 hours under shaking at 4 mg/ml (unless otherwise specified). The injection volume is 300 μl. The top oven temperature where the detectors and injection loop are located at is at 150° C. The temperature profile of CEF is: crystallization at 3° C./min from 110° C. to 30° C., thermal equilibrium at 30° C. for 5 minutes, and elution at 3° C./min from 30° C. to 140° C. The flow rate during crystallization is at 0.052 ml/min. The flow rate during elution is at 0.50 ml/min. The data is collected at one data point/second.

The CEF column is packed by the Dow Chemical Company with glass beads at 125 micron ±6% (MO-SCI Specialty Products) with ⅛ inch stainless tubing. The glass beads are acid washed by MO-SCI Specialty. The column volume is 2.06 ml. The column temperature calibration is performed by using a mixture of NIST Standard Reference Material Linear polyethylene 1475a (1.0 mg/ml) and Eicosane (2 mg/ml) in ODCB. The temperature is calibrated by adjusting the elution heating rate so that the NIST linear polyethylene 1475a has a peak temperature at 101.0° C., and Eicosane has a peak temperature of 30.0° C. The CEF column resolution is calculated with a mixture of NIST linear polyethylene 1475a (1.0 mg/ml) and hexacontane (Fluka, purum, ≧97.0%) (1 mg/ml). A baseline separation of hexacontane and NIST polyethylene 1475a is achieved. The area of hexacontane (from 35.0 to 67.0° C.) to the area of NIST 1475a from 67.0 to 110.0° C. is 50 to 50, and the amount of soluble fraction below 35.0° C. is <1.8 wt %.

The CEF column resolution is defined by Equation 2:

$\begin{matrix} {{Resolution} = \frac{\begin{matrix} {{{Peak}\mspace{14mu} {temperature}\mspace{14mu} {of}\mspace{14mu} {NIST}\mspace{14mu} 1475a} -} \\ {{Peak}\mspace{14mu} {Temperature}\mspace{14mu} {of}\mspace{14mu} {Hexacontane}} \end{matrix}}{\begin{matrix} {{Half} - {{height}\mspace{14mu} {Width}\mspace{14mu} {of}\mspace{14mu} {NIST}\mspace{14mu} 1475a} +} \\ {{Half} - {{height}\mspace{14mu} {Width}\mspace{14mu} {of}\mspace{14mu} {Hexacontane}}} \end{matrix}}} & \left( {{Eq}.\mspace{14mu} 2} \right) \end{matrix}$

The column resolution is 6.0

CDC Method

The comonomer distribution constant (CDC) is calculated from the comonomer distribution profile by CEF. CDC is defined as Comonomer Distribution Index divided by the Comonomer Distribution Shape Factor as shown in Equation 3.

$\begin{matrix} {{CDC} = {\frac{{Comonomer}\mspace{14mu} {Distrubution}\mspace{14mu} {Index}}{{Comonomer}\mspace{14mu} {Distribution}\mspace{14mu} {Shape}\mspace{14mu} {Factor}} = {\frac{{Comonomer}\mspace{14mu} {Distribution}\mspace{14mu} {Index}}{{Half}\mspace{14mu} {{Width}/{Stdev}}}*100}}} & \left( {{Eq}.\mspace{14mu} 3} \right) \end{matrix}$

The comonomer distribution index is the total weight fraction of polymer chains with the comonomer content ranging from 0.5 of the median comonomer content (C_(median)) and 1.5 of the C_(median) from 35.0 to 119.0° C. The Comonomer Distribution Shape Factor is defined as a ratio of the half width of the comonomer distribution profile divided by the standard deviation of the comonomer distribution profile from the peak temperature (T_(p)) further divided by 100.

The CDC is calculated according to the following steps:

Obtain the weight fraction at each temperature (T) (w_(T)(T)) from 35.0° C. to 119.0° C. with a temperature step of 0.200° C. from CEF according Equation 4.

$\begin{matrix} {{\int_{35}^{119.0}{{w_{T}(T)}{T}}} = 1} & \left( {{Eq}.\mspace{14mu} 4} \right) \end{matrix}$

Calculate the median temperature (T_(median)) at a cumulative weight fraction of 0.500 as shown in Equation 5.

$\begin{matrix} {{\int_{35}^{T_{median}}{{w_{T}(T)}{T}}} = 0.5} & \left( {{Eq}.\mspace{14mu} 5} \right) \end{matrix}$

Calculate the corresponding median comonomer content in mole % (C_(median)) at the median temperature (T_(median)) by using the comonomer content calibration curve as shown in Equation 6.

$\begin{matrix} {{\ln \left( {1 - {comonomercontent}} \right)} = {{{- \frac{207.26}{273.12 + T}} + {0.5533\mspace{14mu} R^{2}}} = 0.997}} & \left( {{Eq}.\mspace{14mu} 6} \right) \end{matrix}$

The comonomer content calibration curve is constructed by using a series of reference materials with known amount of comonomer content. Eleven reference materials with narrow comonomer distribution (monomodal comonomer distribution in CEF from 35.0 to 119.0° C.) with weight average molecular weight M_(w) of 35,000 to 115,000 g/mol (by conventional GPC) at a comonomer content ranging from 0.0 mole % to 7.0 mol % are analyzed with CEF at the same experimental conditions as specified in the CEF experimental sections.

The comonomer content calibration is calculated by using the peak temperature (T_(p)) of each reference material and its comonomer content. R² is the correlation constant for the calibration.

The Comonomer Distribution Index is the total weight fraction with a comonomer content ranging from 0.5 mulitplied by C_(median) to 1.5 multiplied by C_(median). If T_(median) is higher than 98.0° C., the Comonomer Distribution Index is defined as 0.95.

The maximum peak height is obtained from the CEF comonomer distribution profile by searching each data point to determine the highest peak from 35.0° C. to 119.0° C. (if two peaks are identical then the lower temperature peak is selected). The half width is defined as the temperature difference between the front temperature and the rear temperature at half of the maximum peak height. The front temperature at half of the maximum peak height is searched forward from 35.0° C., while the rear temperature at half of the maximum peak is searched backward from 119.0° C. In the case of a well defined bimodal distribution where the difference in the peak temperatures is equal to or larger than 1.1 times the sum of half width of each peak, the half-width of the polymer is calculated as the arithmetic average of the half width of each peak.

The standard deviation of temperature (Stdev) is calculated according Equation 7:

$\begin{matrix} {{Stdev} = \sqrt{\sum\limits_{35.0}^{119.0}{\left( {T - T_{p}} \right)^{2}*{w_{T}(T)}}}} & \left( {{Eq}.\mspace{14mu} 7} \right) \end{matrix}$

An example of the comonomer distribution profile for Example 1 is shown in FIG. 1.

Conventional GPC M_(w-gpc) determination

To obtain M_(w-gpc) values, the chromatographic system consist of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220. The column and carousel compartments are operated at 140° C. Three Polymer Laboratories 10-μm Mixed-B columns are used with a solvent of 1,2,4-trichlorobenzene. The samples are prepared at a concentration of 0.1 g of polymer in 50 mL of solvent. The solvent used to prepare the samples contains 200 ppm of the antioxidant butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 4 hours at 160° C. The injection volume used is 100 microliters and the flow rate is 1.0 mL/min Calibration of the GPC column set is performed with twenty one narrow molecular weight distribution polystyrene standards purchased from Polymer Laboratories. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 8:

M _(polyethylene) =A(M _(polystyrene))^(B)  (Eq. 8)

where M is the molecular weight, A has a value of 0.4316 and B is equal to 1.0. A third order polynomial is determined to build the logarithmic molecular weight calibration as a function of elution volume. Polyethylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Version 3.0. The precision of the weight-average molecular weight ΔM_(w) is excellent at <2.6%.

Creep Zero Shear Viscosity Measurement Method

Zero-shear viscosities are obtained via creep tests that are conducted on an AR-G2 stress controlled rheometer (TA Instruments; New Castle, Del.) using 25-mm-diameter parallel plates at 190° C. The rheometer oven is set to test temperature for at least 30 minutes prior to zeroing the fixtures. At the testing temperature a compression molded sample disk is inserted between the plates and allowed to come to equilibrium for 5 minutes. The upper plate is then lowered down to 50 μm above the desired testing gap (1.5 mm) Any superfluous material is trimmed off and the upper plate is lowered to the desired gap. Measurements are done under nitrogen purging at a flow rate of 5 L/min. The default creep time is set for 2 hours.

A constant low shear stress of 20 Pa is applied for all of the samples to ensure that the steady state shear rate is low enough to be in the Newtonian region. The resulting steady state shear rates are in the range of 10⁻³ to 10⁻⁴ s⁻¹ for the samples in this study. Steady state is determined by taking a linear regression for all the data in the last 10% time window of the plot of log (J(t)) vs. log(t), where J(t) is creep compliance and t is creep time. If the slope of the linear regression is greater than 0.97, steady state is considered to be reached, then the creep test is stopped. In all cases in this study the slope meets the criterion within 2 hours. The steady state shear rate is determined from the slope of the linear regression of all of the data points in the last 10% time window of the plot of strain vs. time. The zero-shear viscosity is determined from the ratio of the applied stress to the steady state shear rate.

In order to determine if the sample is degraded during the creep test, a small amplitude oscillatory shear test is conducted before and after the creep test on the same specimen from 0.1 to 100 rad/s. The complex viscosity values of the two tests are compared. If the difference of the viscosity values at 0.1 rad/s is greater than 5%, the sample is considered to have degraded during the creep test, and the result is discarded.

The zero-shear viscosity ratio (ZSVR) is defined as the ratio of the zero-shear viscosity (ZSV) of the branched polyethylene material to the ZSV of the linear polyethylene material at the equivalent weight average molecular weight (Mw-gpc) as shown in the Equation 9.

$\begin{matrix} {{ZSVR} = {\frac{\eta_{0\; B}}{\eta_{0\; L}} = \frac{\eta_{0\; B}}{2.29*10^{- 15}M_{w - {gpc}}^{3.65}}}} & \left( {{Eq}.\mspace{14mu} 9} \right) \end{matrix}$

The ZSV value is obtained from the creep test at 190° C. via the method described above. The Mw-gpc value is determined by the conventional GPC method as described previously. The correlation between the ZSV of linear polyethylene and its Mw-gpc value was established based on a series of linear polyethylene reference materials. A description for the ZSV-Mw relationship can be found in: Karjala, Teresa P.; Sammler, Robert L.; Mangnus, Marc A.; Hazlitt, Lonnie G.; Johnson, Mark S.; Hagen, Charles M., Jr.; Huang, Joe W. L.; Reichek, Kenneth N. “Detection of low levels of long-chain branching in polyolefins.” Annual Technical Conference, Society of Plastics Engineers (2008), 66^(th), p. 887-891.

Melt Strength

Melt strength is measured at 190° C. using a Göettfert Rheotens 71.97 (Göettfert Inc.; Rock Hill, S.C.), melt fed with a Göettfert Rheotester 2000 capillary rheometer equipped with a flat entrance angle (180 degrees) of length of 30 mm and diameter of 2 mm. The pellets are fed into the barrel (L=300 mm, Diameter=12 mm), compressed and allowed to melt for 10 minutes before being extruded at a constant piston speed of 0.265 mm/s, which corresponds to a wall shear rate of 38.2s⁻¹ at the given die diameter. The extrudate passes through the wheels of the Rheotens located at 100 mm below the die exit and is pulled by the wheels downward at an acceleration rate of 2.4 mm/s². The force (in cN) exerted on the wheels is recorded as a function of the velocity of the wheels (in mm/s). Melt strength is reported as the plateau force (cN) before the strand broke.

¹H NMR Method 3.26 g of stock solution is added to 0.133 g of polyolefin sample in 10 mm

NMR tube. The stock solution is a mixture of tetrachloroethane-d₂ (TCE) and perchloroethylene (50:50, w:w) with 0.001M Cr³⁺. The solution in the tube is purged with N₂ for 5 minutes to reduce the amount of oxygen. The capped sample tube is left at room temperature overnight to swell the polymer sample. The sample is dissolved at 110° C. with shaking. The samples are free of the additives that may contribute to unsaturation, e.g. slip agents such as erucamide. The ¹H NMR are run with a 10 mm cryoprobe at 120° C. on Bruker AVANCE 400 MHz spectrometer. The pulse sequence is shown in the Table 1.

TABLE 1 ¹H NMR pulse sequence. ;lc1prf2_zz prosol relations=<lcnmr> #include <Avance.incl> “d12=20u” “d11=4u” 1 ze d12 pl21:f2 2 30m d13 d12 pl9:f1 d1 cw:f1 ph29 cw:f2 ph29 d11 do:f1 do:f2 d12 pl1:f1 p1 ph1 go=2 ph31 30m mc #0 to 2 F0(zd) exit ph1=0 2 2 0 1 3 3 1 ph29=0 ph31=0 2 2 0 1 3 3 1

Two experiments are run to obtain the unsaturation: the control and the double presaturation experiments.

For the control experiment, the data is processed with the exponential window function with LB=1 Hz. The baseline is corrected from 7 to −2 ppm. The signal from the residual ¹H of TCE is set to 100. The integral I_(total) from −0.5 to 3 ppm is used as the signal from the whole polymer in the control experiment. The number of CH₂ groups, NCH₂, in the polymer is calculated from Equation 10:

NCH ₂ =I _(total)/2  (Eq. 10)

For the double presaturation experiment, the data is processed with an exponential window function with LB=1 Hz. The baseline is corrected from 6.6 to 4.5 ppm. The signal from the residual ¹H of TCE is set to 100, the corresponding integrals for unsaturations (I_(vinylene), I_(trisubstituted), I_(vinyl) and I_(vinylidene)) are integrated based on the region shown in FIG. 2. The number of unsaturation units for vinylene, trisubstituted, vinyl and vinylidene are calculated as in Equations 11-14.

N _(vinylene) =I _(vinylene)/2  (Eq. 11)

N_(trisubstituted)=I_(trisubstituted)  (Eq. 12)

N _(vinyl) =I _(vinyl)/2  (Eq. 13)

N _(vinylidene) =I _(vinylidene)/2  (Eq. 14)

The unsaturation unit/1,000,000 carbons is calculated as in Equations 15-18:

N _(vinylene)/1,000,000 C=(N _(vinylene) /NCH ₂)*1,000,000  (Eq. 15)

N _(trisubstitutedd)/1,000,000 C=(N _(trisubstituted) /NCH ₂)*1,000,000  (Eq. 16)

N _(vinyl)/1,000,000 C=(N _(vinyl) /NCH ₂)*1,000,000  (Eq. 17)

N _(vinylidene)/1,000,000 C=(N _(vinylidene) /NCH ₂)*1,000,000  (Eq. 18)

Cross Fractionation: Temperature Rising Elution Fractionation (TREF) Followed by GPC

The experiment is performed with an instrument constructed according to Gillespie and Li Pi Shan et al. (Apparatus for Method for Polymer Characterization, WO2006081116). The data acquisition rate is one data point/second.

TREF Column

The TREF columns are constructed from acetone-washed ⅛ inch×0.085 inch 316 stainless steel tubing. The tubing is cut to a length of 42 inches and packed with a dry mixture (60:40 volume:volume) of pacified 316 stainless steel cut wire of 0.028 inch diameter (Pellet Inc., North Tonawanda, N.Y.) and 30-40 mesh spherical technical grade glass beads. This combination of column length and packing material results in an interstitial volume of approximately 1.75 mL. The TREF column ends are capped with Valco microbore HPLC column end fittings equipped with a 10 μm stainless steel screen. These column ends provide the TREF columns with a direct connection to the plumbing of the cross fractionation instrument within the TREF oven. The TREF columns are coiled, outfitted with an resistance temperature detector (RTD) temperature sensor, and wrapped with glass insulation tape before installation. During installation, extra care is given to level placement of the TREF column with the oven to ensure adequate thermal uniformity within the column Chilled air is provided at 40 L/min to the TREF ovens via a chiller whose bath temperature is 2° C.

TREF Column Temperature Calibration

The reported elution temperatures from the TREF column are adjusted with the heating rate used in the temperature range of 110° C. to 30° C. such that the observed compositions versus elution temperatures agree with those previously reported (L. Wild, R. T. Ryle et al., J. Polymer Science Polymer Physics Edition 20, 441-455 (1982)).

Sample Preparation

The sample solutions are prepared as 4 mg/mL solutions in 1,2,4-trichlorobenzene (TCB) containing 180 ppm butylated hydroxytoluene (BHT) and the solvent is sparged with nitrogen. A small amount of decane is added as a flow rate marker to the sample solution for GPC elution validation. Dissolution of the samples is completed by gentle stirring at 145° C. for four hours.

Sample Loading

Samples are injected via a heated transfer line to a fixed loop injector (Injection loop of 500 mL) directly onto the TREF column at 145° C.

Temperature Profile of TREF Column

After the sample has been injected onto the TREF column, the column is taken “off-line” and allowed to cool. The temperature profile of the TREF column is as follows: cooling down from 145° C. to 110° C. at 2.19° C./min, cooling down from 110° C. to 30° C. at 0.110° C./min, and thermal equilibrium at 30° C. for 16 minutes. During elution, the column is placed back “on-line” to the flow path with a pump elution rate of 0.9 ml/min for 1.0 minute. The heating rate of elution is 0.119° C./min from 30° C. to 110° C.

Elution from TREF Column

The 16 fractions are collected from 30° C. to 110° C. at 5° C. increments per fraction. Each fraction is injected for GPC analysis. Each of the 16 fractions are injected directly from the TREF column over a period of 1.0 minute onto the GPC column set. The eluent is equilibrated at the same temperature as the TREF column during elution by using a temperature pre-equilibration coil (Gillespie and Li Pi Shan et al., Apparatus for Method for Polymer Characterization, WO2006081116). Elution of the TREF is performed by flushing the TREF column at 0.9 ml/min for 1.0 min The first fraction, Fraction (30° C.), represents the amount of material remaining soluble in TCB at 30° C. Fraction (35° C.), Fraction (40° C.), Fraction (45° C.), Fraction (50° C.), Fraction (55° C.), Fraction (60° C.), Fraction (65° C.), Fraction (70° C.), Fraction (75° C.), Fraction (80° C.), Fraction (85° C.), Fraction (90° C.), Fraction (95° C.), Fraction (100° C.), and Fraction (105° C.) represent the amount of material eluting from the TREF column with a temperature range of 30.01 to 35° C., 35.01 to 40° C., 40.01 to 45° C., 45.01 to 50° C., 50.01 to 55° C., 55.01 to 60° C., 60.01 to 65° C., 65.01 to 70° C., 70.01 to 75° C., 75.01 to 80° C., 80.01 to 85° C., 85.01 to 90° C., 90.01 to 95° C., 95.01 to 100° C., and 100.01 to 105° C., respectively.

GPC Parameters

The cross fractionation instrument is equipped with one 20 μm guard column and four Mixed A-LS 20 μm columns (Varian Inc., previously PolymerLabs), and the IR-4 detector from PolymerChar (Spain) is the concentration detector. The GPC column set is calibrated by running twenty one narrow molecular weight distribution polystyrene standards. The molecular weight (MW) of the standards ranges from 580 to 8,400,000 g/mol, and the standards are contained in 6 “cocktail” mixtures. Each standard mixture (“cocktail”) has at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at 0.005 g in 20 mL of solvent for molecular weights equal to or greater than 1,000,000 g/mol and 0.001 g in 20 mL of solvent for molecular weights less than 1,000,000 g/mol. The polystyrene standards are dissolved at 145° C. with gentle agitation for 30 minutes. The narrow standards mixtures are run first and in the order of decreasing highest molecular weight component to minimize degradation. A logarithmic molecular weight calibration is generated using a fourth-order polynomial fit as a function of elution volume. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 19 as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968):

M _(polyethylene) =A(M _(polystyrene))^(B)  (Eq. 19)

where M is the molecular weight, A has a value of 0.40 and B is equal to 1.0.

The plate count for the four Mixed A-LS 20 μm columns needs to be at least 19,000 by using a 200 μl injection volume of a 0.4 mg/ml solution of Eicosane in 1,2,4-Trichlorobenzene (TCB) bypassing the TREF column. The plate count calculates from the peak retention volume (RV_(pk max)) and the retention volume (RV) width at ½ height (50% of the chromatographic peak) to obtain an effective measure of the number of theoretical plates in the column by using Equation 20 (Striegel and Yau et al., “Modern Size-Exclusion Liquid Chromatography”, Wiley, 2009, Page 86):

Plate Count=5.54*[RV _(pk max/() RV _(Rear 50% pk ht) −RV _(Front 50% pk ht))]²  (Eq. 20)

MWD Analysis for Each Fraction

The molecular weight distribution (MWD) of each fraction is calculated from the integrated GPC chromatogram to obtain the weight average molecular weight for each fraction, MW (Temperature).

The establishment of the upper integration limit (high molecular weight end) is based on the visible difference between the peak rise from the baseline. The establishment of the lower integration limit (low molecular weight end) is viewed as the return to the baseline or the point of the elution volume of the polystyrene narrow molecular weight standard of 3250 molecular weight (whichever is earlier).

The white noise level of the IR-4 detector is calculated from the IR-4 detector upon analyzing the GPC chromatogram before the upper integration limit (prior to polymer elution). The detector response at each acquisition time contributed from the polymer chains is first corrected for the baseline correction to obtain the baseline subtracted signal (IR(RV), RV is the elution volume of the GPC chromatogram). The baseline corrected IR-4 response is further corrected for white noise: IR(RV) is used in the GPC calculation only if IR(RV) is larger than the white noise value. In this work, a typical white noise for the IR is determined to be 0.35 mV while the whole-polymer (direct 0.50 mg GPC-injection on the GPC column bypassing the TREF column) peak height in mV is typically around 240 for a polyolefin polymer (high density polyethylene, polydispersity M_(w)/M_(n) approximately 2.6). Care should be maintained to provide a signal to noise ratio (the peak height of whole polymer injection to the white noise) of at least 500 at 1.0 mg/ml 500 μL injection volume for a polyolefin polymer (high density polyethylene, polydispersity M_(w)/M_(n) approximately 2.6).

The area of each individual GPC chromatogram corresponds to the amount of polyolefinic material eluted from the TREF fraction. The weight percentage of the TREF fraction at a specified temperature range of the Fraction, Wt % (Temperature), is calculated as the area of the individual GPC chromatogram divided by the sum of the areas of the 16 individual GPC chromatograms. The GPC molecular weight distribution calculations (Mn, Mw, and Mz) are performed on each chromatogram and reported only if the weight percentage of the TREF fraction is larger than 1.0 wt %. The GPC weight-average molecular weight, Mw, is reported as MW (Temperature) of each chromatogram.

Wt % (30° C.) represents the amount of material eluting from the TREF column at 30° C. during the TREF elution process. Wt % (35° C.), Wt % (40° C.), Wt % (45° C.), Wt % (50° C.), Wt % (55° C.), Wt % (60° C.), Wt % (65° C.), Wt % (70° C.), Wt % (75° C.), Wt % (80° C.), Wt % (85° C.), Wt % (90° C.), Wt % (95° C.), Wt % (100° C.), and Wt % (105° C.) represent the amount of material eluting from the TREF column with a temperature range of 30.01° C. to 35° C., 35.01° C. to 40° C., 40.01 to 45° C., 45.01° C. to 50° C., 50.01° C. to 55° C., 55.01° C. to 60° C., 60.01° C. to 65° C., 65.01° C. to 70° C., 70.01° C. to 75° C., 75.01° C. to 80° C., 80.01° C. to 85° C., 85.01° C. to 90° C., 90.01° C. to 95° C., 95.01° C. to 100° C., and 100.01° C. to 105° C., respectively. The cumulative weight fraction is defined as the sum of the Wt % of the fractions up to a specified temperature. The cumulative weight fraction is 1.00 for the whole temperature range.

The highest temperature fraction molecular weight, MW (Highest Temperature Fraction), is defined as the molecular weight calculated at the highest temperature containing more than 1.0 wt % material. The MW Ratio of each temperature is defined as the MW (Temperature) divided by MW (Highest Temperature Fraction).

Gel Content

Gel content is determined in accordance to ASTM D2765-01 Method A in xylene. The sample is cut to required size using a razor blade.

Film Testing Conditions

The following physical properties are measured on the films produced:

-   -   Total and Internal Haze: Samples measured for total haze and         internal haze are sampled and prepared according to ASTM D 1003.         Internal haze is obtained via refractive index matching using         mineral oil on both sides of the films. A Hazeguard Plus         (BYK-Gardner USA; Columbia, Md.) is used for testing.     -   45° Gloss: ASTM D-2457.     -   MD and CD Elmendorf Tear Strength: ASTM D-1922.     -   MD and CD Tensile Strength: ASTM D-882.     -   Dart Impact Strength: ASTM D-1709.     -   Puncture: Puncture is measured on an Instron Model 4201 with         Sintech Testworks Software Version 3.10. The specimen size is 6         inch×6 inch and 4 measurements are made to determine an average         puncture value. The film is conditioned for 40 hours after film         production and at least 24 hours in an ASTM controlled         laboratory. A 100 lb load cell is used with a round specimen         holder. The specimen is a 4 inch circular specimen. The puncture         probe is a ½ inch diameter polished stainless steel ball (on a         0.25 inch rod) with a 7.5 inch maximum travel length. There is         no gauge length; the probe is as close as possible to, but not         touching, the specimen. The crosshead speed used is 10         inches/minute. The thickness is measured in the middle of the         specimen. The thickness of the film, the distance the crosshead         traveled, and the peak load are used to determine the puncture         by the software. The puncture probe is cleaned using a         “Kim-wipe” after each specimen.     -   Shrink tension is measured according to the method described         in Y. Jin, T. Hermel-Davidock, T. Karjala, M. Demirors, J.         Wang, E. Leyva, and D. Allen, “Shrink Force Measurement of Low         Shrink Force Films”, SPE ANTEC Proceedings, p. 1264 (2008).     -   % Free Shrink: A single layer square film with a dimension of         10.16 cm×10.16 cm is cut out by a punch press from a film sample         along the edges of the machine direction (MD) and the cross         direction (CD). The film is then placed in a film holder and the         film holder is immersed in a hot-oil bath at 150° C. for 30         seconds. The holder is then removed from the oil bath. After oil         is drained out, the length of film is measured at multiple         locations in each direction and the average is taken as the         final length. The % free shrink is determined from Equation 21.

$\begin{matrix} {\frac{\left( {{Initial}\mspace{14mu} {Length}} \right) - \left( {{Final}\mspace{14mu} {Length}} \right)}{{Initial}\mspace{14mu} {Length}} \times 100} & \left( {{Eq}.\mspace{14mu} 21} \right) \end{matrix}$

Production of Examples

All raw materials (ethylene, 1-octene) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent trademarked Isopar E and commercially available from Exxon Mobil Corporation) are purified with molecular sieves before introduction into the reaction environment. Hydrogen is supplied in pressurized cylinders as a high purity grade and is not further purified. The reactor monomer feed (ethylene) stream is pressurized via a mechanical compressor to above reaction pressure at 750 psig. The solvent and comonomer (1-octene) feed is pressurized via a mechanical positive displacement pump to above reaction pressure at 750 psig. The individual catalyst components are manually batch diluted to specified component concentrations with purified solvent (Isopar E) and pressured to above reaction pressure at 750 psig. All reaction feed flows are measured with mass flow meters and independently controlled with computer automated valve control systems.

The continuous solution polymerization reactors consist of two liquid full, non-adiabatic, isothermal, circulating, and independently controlled loops operating in a series configuration. Each reactor has independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The combined solvent, monomer, comonomer and hydrogen feed to each reactor is independently temperature controlled to anywhere between 5° C. to 50° C. and typically 40° C. by passing the feed stream through a heat exchanger. The fresh comonomer feed to the polymerization reactors can be manually aligned to add comonomer to one of three choices: the first reactor, the second reactor, or the common solvent and then split between both reactors proportionate to the solvent feed split. The total fresh feed to each polymerization reactor is injected into the reactor at two locations per reactor roughly with equal reactor volumes between each injection location. The fresh feed is controlled typically with each injector receiving half of the total fresh feed mass flow. The catalyst components are injected into the polymerization reactor through specially designed injection stingers and are each separately injected into the same relative location in the reactor with no contact time prior to the reactor. The primary catalyst component feed is computer controlled to maintain the reactor monomer concentration at a specified target. The two cocatalyst components are fed based on calculated specified molar ratios to the primary catalyst component. Immediately following each fresh injection location (either feed or catalyst), the feed streams are mixed with the circulating polymerization reactor contents with Kenics static mixing elements. The contents of each reactor are continuously circulated through heat exchangers responsible for removing much of the heat of reaction and with the temperature of the coolant side responsible for maintaining an isothermal reaction environment at the specified temperature. Circulation around each reactor loop is provided by a screw pump. The effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the first reactor loop and passes through a control valve (responsible for maintaining the pressure of the first reactor at a specified target) and is injected into the second polymerization reactor of similar design. As the stream exits the reactor it is contacted with water to stop the reaction. In addition, various additives such as anti-oxidants, can be added at this point. The stream then goes through another set of Kenics static mixing elements to evenly disperse the catalyst kill and additives.

Following additive addition, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components. The stream then enters a two stage separation and devolatization system where the polymer is removed from the solvent, hydrogen, and unreacted monomer and comonomer. The recycled stream is purified before entering the reactor again. The separated and devolatized polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transferred into a hopper. After validation of initial polymer properties, the solid polymer pellets are manually dumped into a box for storage. Each box typically holds ˜1200 pounds of polymer pellets.

The non-polymer portions removed in the devolatilization step pass through various pieces of equipment which separate most of the ethylene which is removed from the system to a vent destruction unit (it is recycled in manufacturing units). Most of the solvent is recycled back to the reactor after passing through purification beds. This solvent can still have unreacted co-monomer in it that is fortified with fresh co-monomer prior to re-entry to the reactor. This fortification of the co-monomer is an essential part of the product density control method. This recycle solvent can still have some hydrogen which is then fortified with fresh hydrogen to achieve the polymer molecular weight target.

Tables 2-4 summarize the conditions for polymerization for examples of this invention. Table 5 summarizes catalysts and catalysts components referenced in Table 4.

TABLE 2 Process reactor feeds used to make Examples. 1. REACTOR FEEDS Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Primary Reactor Feed Temperature (° C.) 40.0 40.0 40.0 20.0 20.0 20.0 40.0 40.0 Primary Reactor Total Solvent Flow (lb/hr) 788 710 924 1007 1058 997 869 924 Primary Reactor Fresh Ethylene Flow (lb/hr) 151 117 133 165 184 183 125 161 Primary Reactor Total Ethylene Flow (lb/hr) 158 123 143 174 193 192 134 169 Comonomer Type 1-octene 1-octene 1-octene 1-octene 1-octene 1-octene 1-octene 1-octene Primary Reactor Fresh Comonomer Flow (lb/hr) 0.0 0.0 0.0 0.0 0.0 0.0 3.2 0.0 Primary Reactor Total Comonomer Flow (lb/hr) 14.6 11.9 8.6 32.9 26.1 25.0 7.0 20.7 Primary Reactor Feed Solvent/Ethylene Ratio 5.22 6.07 6.94 6.10 5.74 5.45 6.95 5.73 Primary Reactor Fresh Hydrogen Flow (sccm) 4474 2740 2175 5024 7265 7438 1736 187 Primary Reactor Hydrogen mole % 0.43 0.34 0.23 0.47 0.60 0.63 0.20 0.02 Secondary Reactor Feed Temperature (° C.) 40.2 39.8 40.0 20.3 20.3 19.2 40.2 39.7 Secondary Reactor Total Solvent Flow (lb/hr) 439.6 340.8 327.8 361.8 389.9 418.6 280.7 339.2 Secondary Reactor Fresh Ethylene Flow (lb/hr) 142.0 127.9 118.1 136.1 147.1 157.0 101.1 123.0 Secondary Reactor Total Ethylene Flow (lb/hr) 145.8 131.0 121.4 139.0 150.3 160.6 103.9 125.6 Secondary Reactor Fresh Comonomer Flow 14.3 11.6 6.2 30.8 27.1 20.5 0.0 26.5 (lb/hr) Secondary Reactor Total Comonomer Flow 22.2 17.1 9.2 41.6 36.0 30.3 1.2 33.5 (lb/hr) Secondary Reactor Feed Solvent/Ethylene Ratio 3.10 2.66 2.78 2.66 2.65 2.67 2.78 2.76 Secondary Reactor Fresh Hydrogen Flow (sccm) 2223 2799 4836 593 1223 1008 4136 12466 Secondary Reactor Hydrogen Mole % 0.234 0.327 0.609 0.067 0.128 0.099 0.610 1.497 Secondary Secondary Secondary Secondary Secondary Secondary Primary Secondary Fresh Comonomer injection location Reactor Reactor Reactor Reactor Reactor Reactor Reactor Reactor Ethylene Split (wt %) 52.0 48.5 54.0 55.6 56.3 54.4 56.3 57.3

TABLE 3 Process reaction conditions used to make Examples. 2. REACTION Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Primary Reactor Control Temperature (° C.) 160 160 180 165 140 155 180 155 Primary Reactor Pressure (Psig) 725 725 725 725 725 725 725 725 Primary Reactor Ethylene Conversion (wt %) 74.8 79.4 70.5 72.8 71.3 70.7 90.2 70.0 Primary Reactor FTnIR Outlet [C2] (g/L) 25.1 18.3 23.3 24.0 27.1 28.4 8.0 28.2 Primary Reactor 10log Viscosity (log(cP) 3.21 3.33 2.65 2.76 3.32 2.99 2.67 3.23 Primary Reactor Polymer Concentration (wt %) 12.8 12.2 9.6 11.3 11.5 11.8 12.4 11.2 Primary Reactor Exchanger's Heat Transfer 9.0 9.7 10.3 9.2 7.6 8.5 9.5 7.5 Coefficient (BTU/(hr ft² ° F.)) Primary Reactor Polymer Residence Time (hr) 0.35 0.40 0.31 0.28 0.27 0.28 0.34 0.31 Secondary Reactor Control Temperature (° C.) 190 190 190 190 190 190 190 190 Secondary Reactor Pressure (Psig) 738 741 728 729 731 730 729 729 Secondary Reactor Ethylene Conversion (wt %) 89.7 89.6 88.1 90.2 91.1 88.3 85.2 91.3 Secondary Reactor FTnIR Outlet [C2] (g/L) 7.6 7.7 7.7 6.7 6.3 8.8 7.6 6.1 Secondary Reactor 10log Viscosity (log(cP)) 2.99 3.10 2.55 2.75 2.89 2.85 2.40 2.60 Secondary Reactor Polymer Concentration (wt %) 21.1 20.6 17.4 21.0 21.3 21.3 16.6 21.1 Secondary Reactor Exchanger's Heat Transfer 41.1 39.1 40.2 35.9 35.5 34.3 44.1 38.0 Coefficient (BTU/(hr ft² ° F.)) Secondary Reactor Polymer Residence Time (hr) 0.13 0.15 0.13 0.12 0.11 0.11 0.14 0.13 Overall Ethylene conversion by vent (wt %) 93.7 93.6 92.7 94.2 94.6 92.8 92.7 94.8

TABLE 4 Catalyst conditions used to make Examples. 3. CATALYST Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Primary Reactor: Catalyst Type CAT-A CAT-A CAT-A CAT-A CAT-A CAT-A CAT-A CAT-B Catalyst Flow (lb/hr) 1.90 1.32 0.74 1.11 0.66 0.81 1.60 1.04 Catalyst Concentration (ppm) 17 17 35 18 18 18 35 50 Catalyst Efficiency 3.8 4.5 3.9 6.8 12.4 9.8 2.2 2.4 (Mlbs poly/lb Zr) Catalyst Metal Molecular Weight 90.86 90.86 90.86 90.86 90.86 90.86 90.86 47.38 (g/mol) Co-Catalyst-1 Molar Ratio 1.9 1.6 1.4 1.9 2.1 1.7 1.5 1.2 Co-Catalyst-1 Type RIBS-2 RIBS-2 RIBS-2 RIBS-2 RIBS-2 RIBS-2 RIBS-2 RIBS-2 Co-Catalyst-1 Flow (lb/hr) 0.70 0.45 1.10 0.80 0.43 0.43 1.04 0.46 Co-Catalyst-1 Concentration (ppm) 1153 1153 498 596 596 596 1094 3478 Co-Catalyst-2 Molar Ratio 8.9 9.0 7.0 6.8 6.7 6.9 6.9 5.0 Co-Catalyst-2 Type MMAO-3A MMAO-3A MMAO-3A MMAO-3A MMAO-3A MMAO-3A MMAO-3A MMAO-3A Co-Catalyst-2 Flow (lb/hr) 0.51 0.36 0.54 0.40 0.24 0.29 0.58 0.99 Co-Catalyst-2 Concentration (ppm) 166 166 100 100 100 100 199 148 Secondary Reactor: Catalyst Type CAT-A CAT-A CAT-A CAT-A CAT-A CAT-A CAT-A CAT-A Catalyst Flow (lb/hr) 1.5 1.5 1.6 2.1 2.6 1.9 1.3 2.7 Catalyst Concentration (ppm) 74 74 72 60 60 60 76 74 Catalyst Efficiency 1.8 1.5 1.3 1.7 1.5 2.1 1.0 1.0 (Mlbs poly/lb Zr) Co-Catalyst-1 Molar Ratio 1.5 1.5 1.3 1.5 1.5 1.5 1.2 1.2 Co-Catalyst-1 Type RIBS-2 RIBS-2 RIBS-2 RIBS-2 RIBS-2 RIBS-2 RIBS-2 RIBS-2 Co-Catalyst-1 Flow (lb/hr) 2.0 1.9 4.0 1.4 1.7 1.3 1.5 0.9 Co-Catalyst-1 Concentration (ppm) 1153 1153 498 1799 1799 1799 1094 3478 Co-Catalyst-2 Molar Ratio 7.0 7.0 7.0 7.0 7.0 7.0 6.9 7.0 Co-Catalyst-2 Type MMAO-3A MMAO-3A MMAO-3A MMAO-3A MMAO-3A MMAO-3A MMAO-3A MMAO-3A Co-Catalyst-2 Flow (lb/hr) 1.4 1.4 2.5 2.6 3.2 2.4 1.1 2.8 Co-Catalyst-2 Concentration (ppm) 166 166 100 100 100 100 199 148

TABLE 5 Catalysts and catalyst components detailed nomenclature. Description CAS Name CAT-A Zirconium, [2,2′″-[1,3-propanediylbis(oxy-κO)]bis[3″,5,5″-tris(1,1-dimethylethyl)- 5′-methyl[1,1′:3′,1″-terphenyl]-2′-olato-κO]]dimethyl-, (OC-6-33)- CAT-B [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,3a,8a-η)-1,5,6,7-tetrahydro-2- methyl-s-indacen-1-yl]silanaminato(2-)-κN][(1,2,3,4-η)-1,3-pentadiene]- RIBS-2 Amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) MMAO-3A Aluminoxanes, iso-Bu Me, branched, cyclic and linear; modified methyl aluminoxane

Production of Comparative Example 2

All (co)monomer feeds (ethylene, 1-octene) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent trademarked Isopar E and commercially available from Exxon Mobil Corporation) are purified with molecular sieves before introduction into the reaction environment. High purity hydrogen is supplied by a shared pipeline; it is mechanically pressurized to above reaction pressure at 500 psig prior to delivery to the reactors; and it is not further purified on site other than to remove any potential residual moisture. The reactor monomer feed (ethylene) streams are pressurized via mechanical compressor to above reaction pressure at 500 psig. The solvent feeds are mechanically pressurized to above reaction pressure at 500 psig. The comonomer (1-octene) feed is also mechanically pressurized to above reaction pressure at 500 psig and is injected directly into the feed stream for the first reactor. Three catalyst components are injected into the first reactor (CAT-B, RIBS-2, and MMAO-3A). The RIBS-2 catalyst component is diluted to a predefined concentration at the supplier. The CAT-B and MMAO-3A catalyst components are further batch-wise diluted on site to the desired plant concentration with purified solvent (Isopar E) prior to injection into the reactor. Two catalyst components are injected into the second reactor (Ziegler-Natta premix, and triethylaluminum (TEA)). All catalyst components are independently mechanically pressurized to above reaction pressure at 500 psig. All reactor catalyst feed flows are measured with mass flow meters and independently controlled with positive displacement metering pumps.

The continuous solution polymerization reactors consist of two liquid full, non-adiabatic, isothermal, circulating, and independently controlled loops operating in a series configuration. Each reactor has independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The combined solvent, monomer, comonomer and hydrogen feed to each reactor is independently temperature controlled to anywhere between 10° C. to 50° C. and typically 15° C. by passing the feed stream through a series of heat exchangers. The fresh comonomer feed to the polymerization reactors can be aligned to add comonomer to one of three choices: the first reactor, the second reactor, or the common solvent where it is then split between both reactors proportionate to the shared solvent feed split. In this example the comonomer is fed to the first reactor. The total fresh feed to each polymerization reactor is injected into the reactor at two locations per reactor roughly with equal reactor volumes between each injection location. The fresh feed to the first reactor is controlled typically with each injector receiving half of the total fresh feed mass flow. The fresh feed to the second reactor in series is controlled typically to maintain half of the total ethylene mass flow near each injector, and since the non-reacted ethylene from the first reactor enters the second reactor adjacent to the fresh feed this injector usually has less than half of the total fresh feed mass flow to the second reactor. The catalyst components for the first reactor are injected into the polymerization reactor through specially designed injection stingers and are each separately injected into the same relative location in the first reactor with no contact time prior to the reactor. The catalyst components for the second reactor (Ziegler-Natta and TEA) are injected into the second polymerization reactor through specially designed injection stingers and are each injected into the same relative location in the second reactor.

The primary catalyst component feed for each reactor (CAT-B for the first reactor and a Ziegler-Natta premix for the second reactor) is computer controlled to maintain the individual reactor monomer concentration at a specified target. The cocatalyst components (RIBS-2 and MMAO-3A for the first reactor and TEA for the second reactor) are fed based on calculated specified molar ratios to the primary catalyst component. Immediately following each fresh injection location (either feed or catalyst), the feed streams are mixed with the circulating polymerization reactor contents with Kenics static mixing elements. The contents of each reactor are continuously circulated through heat exchangers responsible for removing much of the heat of reaction and with the temperature of the coolant side responsible for maintaining an isothermal reaction environment at the specified reactor temperature. Circulation around each reactor loop is provided by a screw pump. The effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and dissolved polymer) exits the first reactor loop and passes through a control valve (responsible for controlling the pressure of the first reactor at a specified target) and is injected into the second polymerization reactor of similar design. After the stream exits the second reactor it is contacted with water to stop the reaction (this water is delivered as water of hydration contained with calcium stearate). In addition, various additives such as anti-oxidants (typically Irganox 1010), are also added at this point. The stream then goes through another set of Kenics static mixing elements to evenly disperse the water catalyst kill and any additives.

Following additive addition, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and dissolved polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components. The stream then enters a two stage separation and devolatization system where the polymer is removed from the solvent, hydrogen, and non-reacted monomer and comonomer. The recycled stream is purified before entering the reactor again. The separated and devolatized polymer melt is then combined with a small side stream of additional additives contained within a polymer melt injected into the process by a single screw extruder. These additives (typically Irganox 1076 and Irgafos 168) are mixed with the main process polymer melt by another series of Kenics static mixing element. The fully additive loaded polymer stream then enters a die specially designed for underwater pelletization, is cut into uniform solid pellets, dried, and transferred into a hopper. During transfer to the hopper, a dry blend of fluoroelastomer processing aid is added to the polymer pellet stream.

The non-polymer portions removed in the devolatilization step pass through various pieces of equipment which separate most of the monomer which is removed from the system, cooled, mechanically compressed, and sent via pipeline back to a light hydrocarbons processing plant for reuse. Most of the solvent and comonomer are recycled back to the reactor after passing through purification beds. This solvent can still have non-reacted co-monomer in it that is fortified with fresh co-monomer prior to re-entry to the reactor as previously discussed. This fortification of the co-monomer is an essential part of the product density control method. This recycle solvent can contain some dissolved hydrogen which is then fortified with fresh hydrogen to achieve the polymer molecular weight target. A very small amount of solvent temporarily leaves the system where it is purified and reused or purged from the system as a co-product.

Tables 6-8 summarize the conditions for polymerization for Comparative Example 2 of this invention.

TABLE 6 Process reactor feeds used to make Comparative Example 2. 1. REACTOR FEEDS Primary Reactor Feed Temperature (° C.) 11.9 Primary Reactor Total Solvent Flow (k lb/hr) 105.4 Primary Reactor Fresh Ethylene Flow (k lb/hr) 18.0 Primary Reactor Total Ethylene Flow (k lb/hr) 18.9 Comonomer Type 1-octene Primary Reactor Fresh Comonomer Flow (k lb/hr) 3.1 Primary Reactor Total Comonomer Flow (k lb/hr) 6.3 Primary Reactor Feed Solvent/Ethylene Ratio 5.7 Primary Reactor Fresh Hydrogen Flow (lb/hr) 0.68 Primary Reactor Hydrogen mole % 0.05 Secondary Reactor Feed Temperature (° C.) 11.6 Secondary Reactor Total Solvent Flow (k lb/hr) 54.9 Secondary Reactor Fresh Ethylene Flow (k lb/hr) 21.5 Secondary Reactor Total Ethylene Flow (k lb/hr) 22.0 Secondary Reactor Fresh Comonomer Flow (k lb/hr) 0.0 Secondary Reactor Total Comonomer Flow (k lb/hr) 1.7 Secondary Reactor Feed Solvent/Ethylene Ratio 2.6 Secondary Reactor Fresh Hydrogen Flow (lb/hr) 4.3 Secondary Reactor Hydrogen Mole % 0.28 Fresh Comonomer injection location Primary Reactor Ethylene Split (wt %) 46.2

TABLE 7 Process reactor conditions used to make Comparative Example 2. 2. REACTION Primary Reactor Control Temperature (° C.) 135 Primary Reactor Pressure (Psig) 500 Primary Reactor Ethylene Conversion (wt %) 78.0 Primary Reactor FTnIR Outlet [C2] (g/L) 20.3 Primary Reactor 10log Viscosity (log(cP)) 3.08 Primary Reactor Polymer Concentration (wt %) 13.6 Primary Reactor Exchanger's Heat Transfer Coefficient 42.6 (BTU/(hr ft² ° F.)) Primary Reactor Polymer Residence Time (min) 14.8 Secondary Reactor Control Temperature (° C.) 195 Secondary Reactor Pressure (Psig) 500 Secondary Reactor Ethylene Conversion (wt %) 88.7 Secondary Reactor FTnIR Outlet [C2] (g/L) 8.5 Secondary Reactor 10log Viscosity (log(cP)) 2.95 Secondary Reactor Polymer Concentration (wt %) 20.0 Secondary Reactor Exchanger's Heat Transfer Coefficient 20.4 (BTU/(hr ft² ° F.)) Secondary Reactor Polymer Residence Time (min) 9.0 Overall Ethylene conversion by vent (wt %) 92.8 Total production rate (k lb/hr) 41.0

TABLE 8 Catalyst conditions used to make Comparative Example 2. 3. CATALYST Primary Reactor Catalyst Type CAT-B Primary Reactor Catalyst Flow (lb/hr) 19.0 Primary Reactor Catalyst Concentration (wt %) 0.30 Primary Reactor Catalyst Efficiency (Mlbs poly/lb Ti) 2.6 Primary Reactor Catalyst Metal Molecular Weight (g/mol) 47.9 Primary Reactor Co-Catalyst-1 Molar Ratio 1.2 Primary Reactor Co-Catalyst-1 Type RIBS-2 Primary Reactor Co-Catalyst-1 Flow (lb/hr) 11.0 Primary Reactor Co-Catalyst-1 Concentration (wt %) 1.80 Primary Reactor Co-Catalyst-2 Molar Ratio 1.0 Primary Reactor Co-Catalyst-2 Type MMAO-3A Primary Reactor Co-Catalyst-2 Flow (lb/hr) 3.70 Primary Reactor Co-Catalyst-2 Concentration (wt % Al) 0.10 Secondary Reactor Catalyst Type Ziegler-Natta Secondary Reactor Catalyst Flow (lb/hr) 69.8 Secondary Reactor Catalyst Concentration (ppm Ti) 800 Secondary Reactor Catalyst Efficiency (Mlbs poly/lb Ti) 0.42 Secondary Reactor Co-Catalyst-1 Molar Ratio 5.0 Secondary Reactor Co-Catalyst-1 Type TEA Secondary Reactor Co-Catalyst-1 Flow (lb/hr) 6.6 Secondary Reactor Co-Catalyst-1 Concentration (wt % Al) 2.37

Characterization of Examples and Comparative Examples

Characterization properties of the Examples and Comparative Example 1 (CE1) and Comparative Example 2 (CE2) are given in Table 9. Comparative Example 1 is a ethylene/octene polyethylene produced by a Ziegler-Natta catalyst. The production of Comparative Example 2 was previously described with conditions given in Tables 6-8. The examples are in the general I₂ melt index range of 0.3-0.9 with densities in the range of 0.918 to 0.936 g/cm³. The comparative examples are also in this general melt index and density range. The I₁₀/I₂ range of the examples are from 7.8-14.3. These examples have higher I₁₀/I₂ values or improved processability as compared to the comparative examples with lower I₁₀/I₂ values of 7.4-8.3.

TABLE 9 Melt index (I₂ and I₁₀), melt index ratio (I₁₀/I₂), and density (g/cm³) of Examples and Comparative Examples. Melt Index I₂ at 190° C. Melt Index I₁₀ Density Sample (g/10 min) at 190° C. (g/10 min) I₁₀/I₂ (g/cm³) Ex. 1 0.49 4.6 9.4 0.9276 Ex. 2 0.32 3.4 10.8 0.9279 Ex. 3 0.54 6.0 11.0 0.9341 Ex. 4 0.75 6.4 8.4 0.9180 Ex. 5 0.89 7.5 8.4 0.9247 Ex. 6 0.91 7.1 7.8 0.9248 Ex. 7 0.52 6.2 11.9 0.9357 Ex. 8 0.87 12.4 14.3 0.9262 CE 1 0.52 3.8 7.4 0.9275 CE 2 0.80 6.6 8.3 0.9248

DSC data are given in Table 10. The melting points, percent crystallinities, and cooling temperatures for the Comparative Examples are within the range of these properties shown for the Examples.

TABLE 10 DSC data of melting temperature (T_(m)), heat of fusion, percent crystallinity (% Cryst.), and crystallization temperature (T_(c)) of Examples and Comparative Examples. Heat of Fusion % T_(c) Sample T_(m) (° C.) (J/g) Cryst. (° C.) Ex. 1 121.2 159.8 54.7 109.2 Ex. 2 120.7 161.4 55.3 109.2 Ex. 3 124.7 180.5 61.8 112.4 Ex. 4 116.5 143.9 49.3 103.8 Ex. 5 119.8 157.1 53.8 106.4 Ex. 6 120.2 152.0 52.1 106.2 Ex. 7 125.6 178.9 61.3 113.1 Ex. 8 117.4 163.5 56.0 105.4 CE 1 121.8 156.0 53.4 109.5 CE 2 123.3 169.2 57.9 109.3

DMS viscosity, tan delta, and complex modulus versus phase angle data are given in Tables 11-14, respectively, and plotted in FIGS. 3-5, respectively. The viscosity data of Table 11 and FIG. 3 as well as the viscosity at 0.1 rad/s over that at 100 rad/s in Table 11 show that many of the Examples show high shear thinning behavior of viscosity decreasing rapidly with increasing frequency as compared to the Comparative Examples. From Table 12 and FIG. 4, many of the Examples have low tan delta values or high elasticity as compared to the Comparative Examples. Table 14 and FIG. 5 shows a form of the DMS data which is not influenced as greatly by the overall melt index (MI or I₂) or molecular weight. The more elastic material are lower on this plot (i.e., lower phase angle for a given complex modulus); the Examples are generally lower on this plot or more elastic than the Comparative Examples.

TABLE 11 DMS viscosity data of Examples and Comparative Examples Frequency Viscosity in Pa-s (rad/s) Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 CE 1 CE 2 0.10 21,683 32,760 21,386 12,784 10,115 10,03 125,175 15,698 15,230 13,218 0.16 19,417 28,361 18,839 11,896 9,527 9,477 22,071 13,738 14,688 12,176 0.25 17,238 24,423 16,438 10,934 8,913 8,858 19,079 11,899 14,058 11,146 0.40 15,195 21,002 14,216 9,937 8,274 8,196 16,285 10,236 13,318 10,127 0.63 13,354 17,977 12,224 8,957 7,645 7,532 13,780 8,764 12,502 9,167 1.00 11,663 15,364 10,491 8,026 7,024 6,877 11,558 7,485 11,603 8,279 1.58 10,153 13,083 8,983 7,157 6,412 6,246 9,648 6,371 10,642 7,439 2.51 8,783 11,126 7,677 6,343 5,794 5,633 8,013 5,399 9,628 6,678 3.98 7,571 9,466 6,537 5,617 5,193 5,063 6,670 4,551 8,573 5,927 6.31 6,523 7,951 5,542 4,919 4,570 4,491 5,585 3,804 7,505 5,219 10.00 5,537 6,573 4,660 4,275 3,958 3,943 4,650 3,146 6,458 4,538 15.85 4,620 5,423 3,882 3,672 3,361 3,414 3,866 2,568 5,462 3,890 25.12 3,843 4,412 3,194 3,090 2,780 2,891 3,180 2,066 4,522 3,258 39.81 3,147 3,544 2,597 2,581 2,270 2,426 2,622 1,635 3,670 2,702 63.10 2,543 2,805 2,086 2,117 1,817 1,998 2,139 1,273 2,919 2,197 100.00 2,019 2,195 1,654 1,708 1,424 1,611 1,719 976 2,278 1,755 Viscosity 10.7 14.9 12.9 7.5 7.1 6.2 14.6 16.1 6.7 7.5 0.1/100

TABLE 12 DMS tan delta dataof Examples and Comparative Examples. Tan Delta Freq Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 CE 1 CE 2 0.10 2.76 2.02 2.35 4.27 5.14 5.38 2.27 2.17 7.44 3.94 0.16 2.50 1.90 2.15 3.67 4.52 4.58 2.01 2.01 6.13 3.50 0.25 2.32 1.81 1.99 3.23 4.05 3.99 1.83 1.88 5.31 3.20 0.40 2.18 1.75 1.88 2.91 3.67 3.57 1.68 1.78 4.53 2.96 0.63 2.07 1.70 1.80 2.68 3.35 3.24 1.58 1.71 3.88 2.79 1.00 1.98 1.65 1.74 2.49 3.05 2.98 1.50 1.64 3.34 2.63 1.58 1.89 1.60 1.68 2.34 2.75 2.74 1.45 1.57 2.87 2.47 2.51 1.81 1.54 1.63 2.20 2.46 2.53 1.42 1.50 2.47 2.30 3.98 1.71 1.47 1.56 2.05 2.18 2.31 1.39 1.42 2.15 2.12 6.31 1.60 1.39 1.48 1.91 1.92 2.10 1.37 1.32 1.86 1.93 10.00 1.50 1.30 1.40 1.76 1.69 1.90 1.35 1.22 1.63 1.75 15.85 1.39 1.21 1.30 1.61 1.48 1.71 1.31 1.12 1.42 1.57 25.12 1.28 1.12 1.21 1.46 1.31 1.53 1.26 1.02 1.24 1.41 39.81 1.17 1.04 1.12 1.32 1.16 1.37 1.20 0.93 1.09 1.25 63.10 1.08 0.96 1.03 1.18 1.04 1.22 1.13 0.84 0.96 1.12 100.00 0.98 0.88 0.94 1.06 0.93 1.09 1.05 0.76 0.85 1.00

TABLE 13 Complex modulusand phase angle data of Examples 1 - 5. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Phase Phase Phase Phase Phase G* (Pa) Angle G* (Pa) Angle G* (Pa) Angle G* (Pa) Angle G* (Pa) Angle 2.17E + 03 70.10 3.28E + 03 63.61 2.14E + 03 66.95 1.28E + 03 76.82 1.01E + 03 78.99 3.08E + 03 68.23 4.49E + 03 62.20 2.99E + 03 65.01 1.89E + 03 74.75 1.51E + 03 77.52 4.33E + 03 66.70 6.13E + 03 61.12 4.13E + 03 63.34 2.75E + 03 72.82 2.24E + 03 76.12 6.05E + 03 65.36 8.36E + 03 60.26 5.66E + 03 62.01 3.96E + 03 71.04 3.29E + 03 74.76 8.43E + 03 64.26 1.13E + 04 59.58 7.71E + 03 60.98 5.65E + 03 69.53 4.82E + 03 73.37 1.17E + 04 63.21 1.54E + 04 58.84 1.05E + 04 60.10 8.03E + 03 68.16 7.02E + 03 71.82 1.61E + 04 62.17 2.07E + 04 58.05 1.42E + 04 59.30 1.13E + 04 66.85 1.02E + 04 69.99 2.21E + 04 61.02 2.79E + 04 57.05 1.93E + 04 58.42 1.59E + 04 65.52 1.46E + 04 67.85 3.01E + 04 59.67 3.77E + 04 55.76 2.60E + 04 57.34 2.24E + 04 64.04 2.07E + 04 65.32 4.12E + 04 58.07 5.02E + 04 54.21 3.50E + 04 56.01 3.10E + 04 62.34 2.88E + 04 62.47 5.54E + 04 56.24 6.57E + 04 52.41 4.66E + 04 54.38 4.28E + 04 60.36 3.96E + 04 59.34 7.32E + 04 54.18 8.60E + 04 50.41 6.15E + 04 52.50 5.82E + 04 58.09 5.33E + 04 56.02 9.65E + 04 51.95 1.11E + 05 48.28 8.02E + 04 50.39 7.76E + 04 55.54 6.98E + 04 52.64 1.25E + 05 49.59 1.41E + 05 46.08 1.03E + 05 48.12 1.03E + 05 52.75 9.04E + 04 49.29 1.60E + 05 47.12 1.77E + 05 43.82 1.32E + 05 45.75 1.34E + 05 49.76 1.15E + 05 46.07 2.02E + 05 44.52 2.20E + 05 41.47 1.65E + 05 43.32 1.71E + 05 46.58 1.42E + 05 43.00

TABLE 14 Complex modulus and phase angle data of Examples 6-8 and Comparative Examples 1-2. Ex. 6 Ex. 7 Ex. 8 CE 1 CE 2 Phase Phase Phase Phase Phase G* (Pa) Angle G* (Pa) Angle G* (Pa) Angle G* (Pa) Angle G* (Pa) Angle 1.00E+03 79.47 2.52E+03 66.21 1.57E+03 65.31 1.52E+03 82.35 1.32E+03 75.78 1.50E+03 77.68 3.50E+03 63.58 2.18E+03 63.52 2.33E+03 80.74 1.93E+03 74.07 2.22E+03 75.94 4.79E+03 61.28 2.99E+03 61.99 3.53E+03 79.33 2.80E+03 72.64 3.26E+03 74.33 6.48E+03 59.25 4.07E+03 60.73 5.30E+03 77.57 4.03E+03 71.36 4.75E+03 72.87 8.69E+03 57.61 5.53E+03 59.63 7.89E+03 75.54 5.78E+03 70.27 6.88E+03 71.44 1.16E+04 56.33 7.49E+03 58.65 1.16E+04 73.31 8.28E+03 69.16 9.90E+03 69.97 1.53E+04 55.42 1.01E+04 57.57 1.69E+04 70.80 1.18E+04 67.93 1.41E+04 68.40 2.01E+04 54.80 1.36E+04 56.30 2.42E+04 67.99 1.68E+04 66.49 2.02E+04 66.62 2.66E+04 54.34 1.81E+04 54.76 3.41E+04 65.02 2.36E+04 64.73 2.83E+04 64.56 3.52E+04 53.92 2.40E+04 52.91 4.74E+04 61.79 3.29E+04 62.64 3.94E+04 62.23 4.65E+04 53.39 3.15E+04 50.73 6.46E+04 58.40 4.54E+04 60.23 5.41E+04 59.64 6.13E+04 52.63 4.07E+04 48.27 8.66E+04 54.85 6.17E+04 57.52 7.26E+04 56.82 7.99E+04 51.58 5.19E+04 45.60 1.14E+05 51.20 8.18E+04 54.56 9.66E+04 53.83 1.04E+05 50.21 6.51E+04 42.82 1.46E+05 47.54 1.08E+05 51.45 1.26E+05 50.71 1.35E+05 48.51 8.03E+04 40.01 1.84E+05 43.89 1.39E+05 48.22 1.61E+05 47.48 1.72E+05 46.46 9.76E+04 37.25 2.28E+05 40.31 1.75E+05 44.92

Melt strength data are shown in Table 15 and plotted in FIGS. 6-7. The melt strengths are influenced by the melt index with the melt index in general being higher for lower melt index materials. Examples 1 and 2 have high melt strength values, relatively, as compared to the Comparative Examples.

TABLE 15 Melt strength data Melt Strength (cN) at Sample 190° C. Ex. 1 5.8 Ex. 2 6.9 Ex. 3 5.2 Ex. 4 4.5 Ex. 5 4.0 Ex. 6 3.7 Ex. 7 4.3 Ex. 8 3.4 CE 1 5.6 CE 2 5.1

GPC data for the Examples and Comparative Examples are shown in Table 16 and FIGS. 8-9. In general, the Examples have narrow M_(w)/M_(n) of less than 3.7, excluding Example 8 of a broad M_(w)/M_(n) of 8.9.

TABLE 16 GPC data by conventional GPC M_(w) M_(n) M_(z) Sample (g/mol) (g/mol) M_(w)/M_(n) (g/mol) Ex. 1 109.076 36.814 2.96 243.016 Ex. 2 118.832 41.510 2.86 269.937 Ex. 3 102.200 29.770 3.43 232.600 Ex. 4 100.600 39.880 2.52 201.100 Ex. 5 103.700 28.430 3.65 254.400 Ex. 6 102.500 36.170 2.83 210.800 Ex. 7 96.910 34.420 2.82 193.400 Ex. 8 95.730 10.760 8.90 317.000 CE 1 137.648 35.674 3.86 245.322 CE 2 111.668 29.795 3.75 333.492

Zero shear viscosity (ZSV) data for the Examples and Comparative Examples are shown in Table 17. In general, the Examples have high ZSV ratios as compared to the Comparative Examples.

TABLE 17 Weight average molecular weight Mw from conventional GPC, Zero shear viscosity ZSV, and ZSV Ratio. M_(w) Log (M_(w) Log (ZSV ZSV Sample (g/mol) ZSV (Pa-s) in g/mol) in Pa-s) Ratio Ex. 1 109,076 35,900 5.038 4.555 6.42 Ex. 2 118,832 77,730 5.075 4.891 10.17 Ex. 3 102,200 41,806 5.002 4.621 10.08 Ex. 4 100,600 18,484 5.003 4.267 4.44 Ex. 5 103,700 13,889 5.016 4.143 2.99 Ex. 6 102,500 13,228 5.011 4.121 2.97 Ex. 7 96,910 46,871 4.986 4.671 12.91 Ex. 8 95,730 34,584 4.981 4.539 9.96 CE 1 137,648 17,762 5.139 4.249 1.36 CE 2 111,668 18,399 5.048 4.265 3.02

Unsaturation data for the Examples and Comparative Examples are shown in Table 18. The Examples have very low total unsaturation values as compared to the Comparative Examples. All other unsaturation values (vinylene, trisubstituted, vinyl, and vinylidene) are also lower for the Examples as compared to the Comparative Examples.

TABLE 18 Unsaturation data of Examples and Comparative Examples. Unsaturation Unit/1,000,000 C Trisub- Total Unsaturation/ Sample Vinylene stituted Vinyl Vinylidene 1,000,000 C Ex. 1 9 6 51 6 72 Ex. 2 5 1 54 5 66 Ex. 3 10 0 68 4 82 Ex. 4 8 3 56 12 79 Ex. 5 8 2 48 9 67 Ex. 6 11 3 62 8 84 Ex. 7 5 1 59 6 70 Ex. 8 26 18 45 14 103 CE 1 35 46 179 20 280 CE 2 39 47 179 20 285

Short chain branching distribution data are shown in Table 19 and FIGS. 10-11. The Examples have higher CDC and Comonomer Distribution Index than the Comparative Examples. The Examples have a monomodal or bimodal distribution excluding the soluble fraction at temperature ˜30° C.

TABLE 19 Summary of CEF data of Examples and Comparative Examples. CDC(Como- Comonomer Stdev HalfWidth HalfWidth/ nomer Dist. Sample Dist. Index (° C.) (° C.) Stdev Constant) Ex. 1 0.5617 8.191 3.057 0.373 150.5 Ex. 2 0.6329 7.228 2.913 0.403 157.0 Ex. 3 0.6490 5.957 3.261 0.547 118.6 Ex. 4 0.5482 15.052 6.197 0.412 133.2 Ex. 5 0.3380 15.327 6.420 0.419 80.7 Ex. 6 0.5698 10.725 3.211 0.299 190.3 Ex. 7 0.8517 2.592 2.761 1.065 80.0 Ex. 8 0.5712 16.598 8.305 0.500 114.2 CE 1 0.1989 18.289 4.902 0.268 74.2 CE 2 0.1960 18.039 4.887 0.271 72.4

The MW Ratio is measured by cross fractionation (TREF followed by GPC) for the Examples and Comparative Examples. The MW Ratio is shown in Tables 20 and 21 and FIGS. 12-13. The Examples have MW Ratio values increasing from a low value (close to 0.10) with temperature, and reaching a maximum value of 1.00 at the highest temperature with these values monotonically increasing. The Comparative Examples having MW Ratio values larger than 1.00 for some temperatures and some MW Ratios at higher temperatures being lower than MW Ratio values at lower temperatures. In addition, the Examples have MW Ratios for the temperatures ≦50° C. of less than 0.10, while the Comparative Examples have MW Ratios larger than 0.10 for some temperatures ≦50° C. The Examples have a cumulative weight fraction less than 0.10 for the temperature fractions up to 50° C.

TABLE 20 MW Ratio of Examples 1-5. Fraction 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Temp (° C.) 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 Ex. Wt % 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.5% 0.8% 2.0% 4.3% 10.5% 17.6% 14.1% 48.2% 2.1% 0.0% 1 (Temp) Cum. wt. 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.03 0.08 0.18 0.36 0.50 0.98 1.00 1.00 frac. MW Ratio 0.07 0.08 0.14 0.21 0.34 0.56 1.00 Ex. Wt % 0.0% 0.1% 0.0% 0.1% 0.1% 0.1% 0.2% 0.4% 0.9% 2.3% 6.9% 15.8% 16.3% 48.4% 8.4% 0.0% 2 (Temp) Cum. wt. 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02 0.04 0.11 0.27 0.43 0.92 1.00 1.00 frac. MW Ratio 0.06 0.12 0.20 0.32 0.59 1.00 Ex. Wt % 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.3% 0.4% 0.5% 1.1% 2.6% 6.4% 9.2% 73.7% 5.4% 3 (Temp) Cum. wt. 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02 0.05 0.11 0.20 0.94 1.00 frac. MW Ratio 0.04 0.06 0.09 0.19 0.60 1.00 Ex. Wt % 0.3% 0.1% 0.3% 0.5% 1.0% 1.9% 3.5% 6.4% 11.0% 17.0% 9.3% 3.4% 42.6% 2.6% 0.0% 4 (Temp) Cum. wt. 0.00 0.00 0.007 0.013 0.02 0.04 0.08 0.14 0.25 0.42 0.51 0.55 0.97 1.00 1.00 frac. MW Ratio 0.10 0.14 0.19 0.25 0.28 0.35 0.43 0.69 1.00 Ex. Wt % 0.2% 0.2% 0.3% 0.4% 0.8% 1.4% 2.4% 4.1% 7.1% 12.3% 15.8% 6.5% 8.5% 34.1% 6.0% 0.0% 5 (Temp) Cum. wt. 0.00 0.00 0.01 0.0120 0.02 0.03 0.06 0.10 0.17 0.29 0.45 0.51 0.60 0.94 1.00 1.00 frac. MW Ratio 0.04 0.05 0.07 0.10 0.13 0.17 0.20 0.59 0.65 1.00

TABLE 21 MW Ratio of Examples 6-8 and Comparative Examples 1-2. Fraction 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Temp (° C.) 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 Ex. Wt % 0.1% 0.0% 0.1% 0.1% 0.2% 0.3% 0.5% 1.2% 2.7% 6.6% 15.7% 17.6% 11.7% 41.2% 2.0% 0.0% 6 (Temp) Cum. wt. 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02 0.05 0.12 0.27 0.45 0.57 0.98 1.00 1.00 frac. MW Ratio 0.08 0.12 0.20 0.25 0.54 0.64 1.00 Ex. Wt % 0.0% 0.0% 0.0% 0.0% 0.0% 0.1% 0.0% 0.1% 0.2% 0.3% 0.5% 1.2% 3.8% 78.4% 15.2% 0.2% 7 (Temp) Cum. wt. 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02 0.06 0.85 1.00 1.00 frac. MW Ratio 0.08 0.21 0.72 1.00 Ex. Wt % 2.7% 0.5% 0.8% 1.1% 1.7% 2.5% 3.9% 6.2% 9.7% 13.8% 9.7% 4.8% 40.2% 2.3% 0.1% 0.0% 8 (Temp) Cum. wt. 0.03 0.03 0.04 0.05 0.07 0.09 0.13 0.19 0.29 0.43 0.53 0.57 0.98 1.00 1.00 1.00 frac. MW Ratio 0.01 0.02 0.03 0.03 0.04 0.05 0.06 0.09 0.13 0.28 0.69 1.00 CE1 Wt % 6.7% 0.9% 1.3% 2.2% 3.5% 4.5% 6.2% 7.8% 10.2% 11.8% 12.3% 9.6% 5.3% 10.3% 7.2% 0.3% (Temp) Cum. wt. 0.07 0.08 0.09 0.11 0.15 0.19 0.25 0.33 0.43 0.55 0.67 0.77 0.82 0.92 1.00 1.00 frac. MW Ratio 0.23 0.13 0.20 0.25 0.31 0.37 0.41 0.46 0.53 0.50 0.65 0.62 0.72 1.00 CE2 Wt % 2.1% 0.2% 0.4% 0.8% 0.5% 0.8% 1.2% 2.9% 10.1% 22.0% 7.4% 5.2% 6.1% 20.2% 17.6% 2.6% (Temp) Cum. wt. 0.02 0.02 0.03 0.03 0.04 0.05 0.06 0.09 0.19 0.41 0.48 0.54 0.60 0.80 0.97 1.00 frac. MW Ratio 0.91 0.23 0.43 0.88 1.24 1.08 0.31 0.31 0.55 0.75 1.00

Production of Films

Films are made on a 6 inch die with a linear low density (LLDPE) type screw. During film fabrication, no internal bubble cooling is used. Several different series of samples are made. Films are made of 100% of the Examples and Comparatives Examples. Films of blends of the Examples and Comparative Examples with a high pressure low density polyethylene, Dow high pressure low density polyethylene (LDPE) LDPE 132I (0.25 MI, 0.921 g/cm³) are also made. Two different types of blends are made: a) LLDPE-rich with 65 wt % linear low density polyethylene or LLDPE (the Examples and Comparative Examples) and 35 wt % LDPE 132I and b)

LDPE-rich with 80% wt LDPE 132I and 20 wt % LLDPE (the Examples and Comparative Examples).

General blown film parameters used to produce the blown films for the LLDPE-rich films are shown in Table 22. The temperatures in Table 22 show the temperatures closest to the pellet hopper (Barrel 1) and in increasing order as the polymer is being extruded through the die (upper die).

The film properties of the LLDPE-rich samples are shown in Table 23-26. LLDPE-rich film Set 1 made under film process conditions shown in Table 22 are shown in Tables 23-24. Examples 3-8 show good MD and CD shrink tension and free shrink, which is advantageous for use in shrink film, good optics (haze, gloss, clarity), and generally good film properties (puncture, dart, and tear).

Table 25-26 show data for Examples 1 and 2 (LLDPE-Rich Film Set 2 in Table 22) as compared to Comparative Examples 1-2. Examples 1-2 show good MD and CD shrink tension and free shrink, which is advantageous for use in shrink film, good optics (haze, gloss, clarity), and generally good film properties (puncture, dart, and tear).

The film properties of the LDPE-rich samples are shown in Tables 27-28. The Examples show good MD and CD shrink tension and free shrink, which is advantageous for use in shrink film, good optics (haze, gloss, clarity), and generally good film properties (puncture, dart, and tear). The Examples show higher shrink tension coupled with higher puncture and good haze, while maintaining a high secant modulus as compared to the Comparative Examples.

TABLE 22 Blown film process parameters used to produce all films. LLDPE- LLDPE- Rich Rich LDPE- Film Film Rich LLDPE LLDPE Set 1 Set 2 Films 0.5 MI 0.85 MI Parameter Blow up ratio 2.5 2.5 2.5 2.5 2.5 (BUR) Output (lb/hr) 150 150 150 150 150 Film Thickness 2 2 2 2 2 (mil) Die Gap (mil) 70 70 70 70 70 Layflat (in) 23.5 23.5 23.5 23.5 23.5 Air Temperature 45 45 45 45 45 (° F.) Temperature Profile (° F.) Barrel 1 375 375 375 375 375 Barrel 2 425 425 425 425 420 Barrel 3 420 350 420 410 370 Barrel 4 420 350 420 400 340 Barrel 5 420 350 420 400 310 Screen 440 450 440 450 460 Adapter 440 450 440 450 460 Rotator 440 450 440 450 460 Lower Die 450 450 450 450 460 Upper Die 450 450 450 450 460

TABLE 23 Film properties of LLDPE-rich film Set 1 (65% LLDPE/35% LDPE) excluding tensile properties. MD CD MD CD Gloss Shrink Shrink Free Free Haze Haze 45 Puncture Dart MD CD I₂ I₁₀/I₂ Tension Tension Shrink Shrink Total Internal Degree Clarity (ft- A Tear Tear (190° (190° Density Sample (Psi) (Psi) 150° C. 150° C. (%) (%) (%) (%) lb/in³) (g) (g) (g) C.) C.) (g/cm³) Ex. 3 18.9 1.3 78.3 17.3 14.5 3.9 56 94 87 112 76 749 0.34 12.7 0.9316 Ex. 4 21.1 0.8 79.3 19.3 13.9 2.8 54 91 81 154 110 918 0.50 13.9 0.9244 Ex. 5 21.7 0.7 79.3 12.4 10.9 2.3 64 93 124 346 113 1,001 0.50 10.7 0.9242 Ex. 6 15.7 0.8 77.4 14.4 10.9 2.9 63 94 126 178 118 927 0.49 10.2 0.9251 Ex. 7 15.1 1.0 76.4 21.3 15.6 5.4 56 95 76 112 131 726 0.35 13.4 0.9328 Ex. 8 16.7 1.0 78.3 20.3 10.9 1.8 62 94 202 157 186 1,072 0.45 11.3 0.9202 CE 1 26.2 0.8 77.4 10.4 9.2 2.9 75 91 88 265 173 1,490 0.32 9.8 0.9265 CE 2 18.3 0.2 78.3 16.3 12.0 2.8 61 93 150 301 176 1,337 0.45 10.6 0.9243

TABLE 24 Film properties of LLDPE-rich film Set 1 (65% LLDPE/35% LDPE): tensile properties. 2% Secant 2% Secant Break Break Strain at Strain at Strain at Strain at Stress at Stress at Modulus Modulus Stress Stress Break Break Yield Yield Yield Yield Sample MD (Psi) CD (Psi) MD (Psi) CD (Psi) MD (%) CD (%) MD (%) CD (%) MD (Psi) CD (Psi) Ex. 3 51,731 63,048 5,385 5,022 592 849 103 11 3,227 2,595 Ex. 4 30,507 36,500 4,282 4,587 416 763 25 14 2,253 2,211 Ex. 5 32,111 36,964 4,721 3,486 531 661 90 11 3,044 1,947 Ex. 6 33,844 39,572 4,036 2,335 429 503 37 58 2,099 1,714 Ex. 7 52,074 63,114 4,985 4,901 571 822 125 12 3,012 2,633 Ex. 8 25,857 28,979 4,800 4,062 484 618 99 13 2,759 1,665 CE 1 40,344 47,793 5,002 4,585 496 666 86 14 3,048 1,908 CE 2 36,319 43,677 4,480 3,834 501 612 120 21 2,642 1,825

TABLE 25 Film properties of LLDPE-rich film Set 2 (65% LLDPE/35% LDPE) excluding tensile properties. MD CD MD CD Gloss Shrink Shrink Free Free Haze Haze 45 Puncture Dart MD CD I₂ I₁₀/I₂ Tension Tension Shrink Shrink Total Internal Degree Clarity (ft- A Tear Tear (190° (190° Density Sample (Psi) (Psi) 150° C. 150° C. (%) (%) (%) (%) lb/in³) (g) (g) (g) C.) C.) (g/cm³) Ex. 1 22.8 0.9 80.3 20.3 12.5 3.1 50 94 128 145 94 989 0.33 11.6 0.9263 Ex. 2 24.7 1.3 81.3 21.3 13.0 2.4 47 77 128 169 89 976 0.23 12.6 0.9263 CE 1 29.5 0.6 80.3 8.5 9.9 2.5 60 89 83 310 163 1,462 0.33 9.6 0.9256 CE 2 14.2 0.7 78.3 18.3 11.4 3.1 57 94 155 310 218 1,329 0.55 10.4 0.9249

TABLE 26 Film properties of LLDPE-rich film Set 2 (65% LLDPE/35% LDPE): tensile properties. 2% Secant 2% Secant Break Break Strain at Strain at Strain at Strain at Stress at Stress at Modulus Modulus Stress Stress Break Break Yield Yield Yield Yield Sample MD (Psi) CD (Psi) MD (Psi) CD (Psi) MD (%) CD (%) MD (%) CD (%) MD (Psi) CD (Psi) Ex. 1 35,963 42,716 5,908 5,292 593 837 14 13 2,181 2,148 Ex. 2 35,921 42,147 6,150 4,806 541 762 15 30 2,219 2,137 CE 1 34,146 40,191 5,163 4,197 474 754 16 13 2,070 1,574 CE 2 34,232 42,470 5,046 5,105 515 731 13 11 1,860 1,940

TABLE 27 Film properties of LDPE-rich films (80% LDPE/20% LLDPE) excluding tensile properties. MD CD MD % CD % Gloss Shrink Shrink Free Free Haze Haze 45 Puncture Dart MD CD I₂ I₁₀/I₂ Tension Tension Shrink Shrink Total Internal Degree Clarity (ft- A Tear Tear (190° (190° Density Example (Psi) (Psi) (150° C.) (150° C.) (%) (%) (%) (%) lb/in³) (g) (g) (g) C.) C.) (g/cm³) Ex. 1 32.1 0.8 83.3 23.2 12.4 1.8 47.6 86.5 71 172 212 339 0.23 16.4 0.9228 Ex. 2 34.4 0.7 83.3 23.2 12.6 1.9 46.6 86.9 80 169 206 387 0.22 16.0 0.9227 Ex. 3 31.9 0.8 80.3 25.2 10.9 2.2 64.0 91.8 65 130 246 310 0.18 18.5 0.9251 Ex. 4 33.4 1.4 80.3 26.2 10.6 1.4 63.4 91.0 94 238 153 394 0.24 16.8 0.9215 Ex. 5 30.7 1.0 80.3 26.2 11.0 1.5 63.4 89.5 86 157 193 311 0.26 16.5 0.9225 Ex. 6 32.1 0.8 82.3 25.2 10.6 1.7 65.0 91.4 86 190 174 331 0.26 16.8 0.9232 Ex. 7 25.6 0.9 78.3 29.1 12.1 2.4 60.4 91.3 70 124 251 327 0.22 17.7 0.9248 Ex. 8 28.5 1.2 81.3 26.2 11.0 1.5 62.8 90.6 80 148 179 314 0.30 17.3 0.9226 CE 1 37.0 0.7 82.3 23.2 12.4 1.2 45.9 83.3 52 250 142 360 0.22 14.6 0.9230 CE 2 27.8 0.4 81.3 24.2 10.6 1.6 52.3 90.0 92 160 197 439 0.29 16.8 0.9234

TABLE 28 Film properties of LDPE-rich films (80% LDPE/20% LLDPE): tensile properties. 2% Secant 2% Secant Break Break Strain at Strain at Strain at Strain at Stress at Stress at Modulus Modulus Stress Stress Break Break Yield Yield Yield Yield Example MD (Psi) CD (Psi) MD (Psi) CD (Psi) MD (%) CD (%) MD (%) CD (%) MD (Psi) CD (Psi) Ex. 1 29,900 35,489 4,354 4,214 321 711 14 13 1,743 1,874 Ex. 2 26,016 34,923 4,222 3,991 294 720 13 13 1,742 1,782 Ex. 3 37,253 42,344 4,251 3,480 289 653 93 26 3,519 1,852 Ex. 4 32,372 36,897 4,665 3,852 387 639 113 12 3,347 1,591 Ex. 5 34,594 38,215 4,380 3,532 318 625 57 19 2,949 1,694 Ex. 6 35,086 39,124 4,025 3,620 299 637 57 15 2,802 1,710 Ex. 7 37,170 43,450 4,086 3,698 335 643 103 14 3,186 1,892 Ex. 8 33,656 37,261 3,626 3,427 243 634 75 13 2,803 1,666 CE 1 28,502 35,793 4,136 3,277 242 631 13 28 1,705 1,692 CE 2 28,037 34,739 2,419 4,483 276 706 22 14 1,069 2,002

TABLE 29 Film properties of 100% LLDPE films excluding tensile properties. MD CD MD CD Gloss Shrink Shrink Free Free Haze Haze 45 Puncture Dart MD CD I₂ I₁₀/I₂ Tension Tension Shrink Shrink Total Internal Degree Clarity (ft- A Tear Tear (190° (190° Density (Psi) (Psi) 150 C. 150 C. (%) (%) (%) (%) lb/in³) (g) (g) (g) C.) C.) (g/cm³) Ex. 1 4.4 0.8 66.5 18.3 11.5 4.4 59 99 168 190 424 995 0.47 9.5 0.9283 Ex. 2 6.1 1.1 73.4 19.3 13.8 4.3 49 99 182 280 388 1,128 0.33 10.4 0.9275 Ex. 3 5.6 0.7 70.5 3.5 16.2 6.8 59 99 101 130 71 802 0.53 10.8 0.9355 Ex. 4 5.4 0.4 69.5 −3.3 9.3 4.3 78 99 304 496 631 1,188 0.76 8.4 0.9190 Ex. 5 5.4 0.2 67.5 −3.3 19.2 7.7 53 97 149 127 427 1,248 0.89 8.4 0.9256 Ex. 6 5.2 0.4 67.5 −8.3 22.1 7.5 50 96 170 226 415 1,045 0.90 8.0 0.9264 Ex. 7 5.7 0.9 74.4 11.4 16.8 7.5 63 99 99 139 64 609 0.59 11.3 0.9372 Ex. 8 6.3 0.5 76.4 6.5 13.2 5.2 65 98 124 112 227 1,525 1.00 13.4 0.9266 CE 1 3.7 0.3 55.7 1.6 9.5 4.5 74 90 99 379 614 1,053 0.52 7.4 0.9278 CE 2 3.9 0.5 73.4 0.6 14.8 6.7 56 99 207 598 541 1,050 0.94 7.9 0.9256

TABLE 30 Film properties of 100% LLDPE films: tensile properties. 2% Secant 2% Secant Break Break Strain at Strain at Strain at Strain at Stress at Stress at Modulus Modulus Stress Stress Break Break Yield Yield Yield Yield MD (Psi) CD (Psi) MD (Psi) CD (Psi) MD (%) CD (%) MD (%) CD (%) MD (Psi) CD (Psi) Ex. 1 42,202 40,752 18,889 3,174 734 696 31 50 7,058 1,578 Ex. 2 38,209 39,996 4,236 17,797 708 744 22 19 1,308 6,571 Ex. 3 59,224 67,810 6,900 2,543 747 909 15 13 2,543 2,699 Ex. 4 23,684 25,874 6,965 1,695 653 773 93 20 1,695 1,456 Ex. 5 33,843 36,243 5,150 1,848 664 860 63 18 1,848 1,826 Ex. 6 35,951 40,700 5,883 1,953 658 720 32 45 1,953 1,898 Ex. 7 60,601 67,561 3,527 3,445 215 718 90 39 3,445 2,432 Ex. 8 34,344 37,956 4,254 1,849 637 792 19 14 1,849 2,024 CE 1 37,210 44,259 2,438 4,528 604 649 30 37 905 2,399 CE 2 33,493 39,329 6,544 6,246 656 726 23 15 1,894 2,133 

1. An ethylene-based polymer composition characterized by a Comonomer Distribution Constant greater than about 45 and as high as 400, wherein the composition has less than 120 total unsaturation unit/1,000,000 C, wherein the composition is further characterized as comprising a MW Ratio at each temperature is less than or equal to 1.00 for each fraction comprising more than 1.0 wt % which represents the area of the fraction divided by the total area of all fractions.
 2. The composition of claim 1 further comprising a melt index of less than or equal to 0.90 g/10 min.
 3. The composition of claim 1 further comprising a density of less than 0.945 g/cc and greater than 0.92 g/cc.
 4. The composition of claim 1 further comprising a density of greater than 0.92 g/cc and less than 0.94 g/cc.
 5. The composition of claim 1 wherein the MW Ratio increases with the temperature of each fraction.
 6. The composition of claim 1 wherein the MW Ratio is less than 0.10 for each temperature that is equal to or lower than 50° C.
 7. The composition of claim 1 wherein the cumulative weight fraction is less than 0.10 for the fractions with a temperature up to 50° C.
 8. The composition of claim 1 wherein the cumulative weight fraction is not less than 0.03 for the fractions with a temperature up to 85° C.
 9. The composition of claim 1 wherein the composition is further characterized as comprising: (d) one Component A being 20-65 wt % of the composition with a MI less than 0.3 and has a higher density than Component B with a density difference between Component B and A of greater than 0.005 g/cc (e) Component B having a MI greater than that of Component A (f) With the overall polymer having a MI of less than or equal to 0.9 and a density of less than 0.945 g/cc and greater than 0.92 g/cc.
 10. The polymer composition of claim 1 wherein the composition comprises up to about 3 long chain branches/1000 carbons.
 11. The polymer composition of claim 1 having a ZSVR of at least 2.5.
 12. The polymer composition of claim 1 having a ZSVR of at least
 4. 13. The polymer of claim 1 further characterized by comprising less than 20 vinylidene unsaturation unit/1,000,000 C.
 14. The polymer of claim 1 further characterized by comprising less than 20 trisubstituted unsaturation unit/1,000,000 C.
 15. The polymer composition of claim 1 wherein the composition has a bimodal molecular weight distribution.
 16. The polymer composition of claim 1 further comprising a single DSC melting peak.
 17. A fabricated article comprising the composition of claim
 1. 18. A thermoplastic formulation comprising the composition of claim 1 and at least one natural or synthetic polymer.
 19. The formulation of claim 18 wherein the synthetic polymer is LDPE and the % LDPE is greater than 30% in which in which a blown film comprising the formulation has a MD shrink tension is greater than 15 cN, puncture is greater than 60 ft-lb/in³, and haze is less than 20%.
 20. The composition of claim 1 wherein the composition has a comonomer distribution profile comprising a mono or bimodal distribution from 35° C. to 120° C., excluding the purge.
 21. The polymer composition of claim 1 comprising Mw from about 80,000 to about 200,000 g/mol.
 22. The fabricated article of claim 17 in the form of at least one film layer.
 23. The polymer composition of claim 1 characterized as having a ratio of viscosity at 190° C. at 0.1 rad/s to a viscosity at 190° C. at 100 rad/s of greater than 8.5 as determined by dynamic mechanical spectroscopy.
 24. The polymer composition of claim 1 characterized as having a phase angle of less than 65 degrees and greater than 0 degrees at a complex modulus of 10,000 Pa as determined by dynamic mechanical spectroscopy at 190° C.
 25. The polymer composition of claim 1 characterized as having a M_(w)/M_(n) less than
 10. 26. The polymer composition of claim 1 characterized as having a M_(w)/M_(n) less than
 4. 